ROSEMARY ANTIOXIDANT MARKET STUDIES

TABLE OF CONTENTS

OVERVIEW1. INTRODUCTION

1.1. Rosemary 1.2. Antioxidants

2. IMPORTANCE_OF_THE_INDUSTRY 2.1. The_science_of_oxidation 2.2. Measurement_of_antioxidant_activity

3. BIOLOGICAL_ANTIOXIDANTS 3.1. The_search_for_new_substances 3.2. Rosemary_antioxidants 3.3. Other_natural_antioxidants

3.3.1. Tocopherol 3.3.2. Carotenoid 3.3.3. Polyphenol_Flavonoid 3.3.4. Ascorbic_acid 3.3.5. Glutathione 3.3.6. Selenium

4. CROP_PRODUCTION_AND_RESEARCH 4.1. UK 4.2. Spain 4.3. France 4.4. Germany 4.5. Italy 4.6. Morocco 4.7. Tunisia 4.8. Israel 4.9. Canada

5. DESCRIPTION_OF_ANTIOXIDANT_INDUSTRY 5.1. MARKETS_BY_PRODUCT_TYPE

5.1.1. Food 5.1.2. Pharmaceuticals 5.1.3. Nutraceuticals 5.1.4. Cosmetics 5.1.5. Plastics_and_Lubricants

6. COMPANIES 6.1. European_companies ADMBFA_laboratoriesChr_HansenCiba_Speciality_ChemicalsDaniscoBordasGrupo_NatraFlavex

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IFF_Bush_Boake_AllenJan_DekkerMonteloederFuresaNaturexNestleVitiva RAD_Natural_TechnologiesRAPS_GmbHEuro_IngredientsProvital_SASYMRISE6.2. North_American_Companies EcomHauserBInutraceuticalsKalsecKeminNewly_Weds_FoodsNoracRFI_IngredientsSabinsa_Corporation

7. EXTRACTION 7.1. Conventional_solvent 7.2. Supercritical_CO2 7.3. Mechanical_extraction_under_pressure 7.4. Ultrasonic_assisted_solvent_extraction 7.5. Patents

8. REGULATION_AND_LEGISLATION 8.1. Foods

8.1.1. European_Food_Safty_Authority 8.1.2. Food_and_Drug_Administration

8.2. Nutritional_supplements_Herbal_medicines 8.2.1. EU_Food_Supplements_Directive 8.2.2. Traditional_Herbal_Medicines_Directive 8.2.3. DSHEA

8.3. Animal_Feed 8.4. Cosmetic_Products

9. TREATS_TO_UK_AND_EUROPEAN_PRODUCTION 9.1. Low_cost_producers

9.1.1. China 9.1.2. India 9.1.3. South_America 9.1.4. Eastern_Europe 9.1.5. Turkey 9.1.6. North_Africa 9.1.7. Australia

9.2. Contra_indications 10. SWOT_ANALYSIS 11. CONCLUSION

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12. REFERENCES 13. WEB_SITES

OVERVIEW

Antioxidants are compounds, which reduce the rate of oxidation so preventing

product deterioration. Antioxidants find applications in foods, animal feed,

pharmaceuticals, nutraceuticals, cosmetics, plastics and lubricants. The types of

antioxidants used in a particular market sub-sector are fairly well established.

Restrictions in application are generally limited to cost, effectiveness, stability within

a given system, and the minimization of undesirable effects such as discoloration.

Additional regulations governing health and safety exist within the food and

nutraceutical markets and, to a lesser extent, in cosmetics.

The goal of this review is to consolidate information about the biological and

rosemary antioxidant market in particular, in one concise and detailed study.

Objectives include an overview of natural antioxidants, potential markets, major

producers and suppliers, methods of extraction and differences in regulation,

legislation in the EC and the US and potential threat to production in the UK.

Market research indicates that there is a demand for rosemary extract as an

antioxidant and the present estimate of the worldwide value of the market is between

£70-90 million. This market would require the production of 60,000 ha of rosemary

assuming a price of £30/kg for 4% extract and a content of carnosic acid of 2.5%,

50kg/ha. The carnosic acid content of selected accessions grown in the UK are

typically 4% and above much higher than those traditionally imported from Spain and

North Africa which have carnosic acid concentrations of 1%.

There are already a number of companies in Europe and the US extracting, marketing

and using rosemary antioxidants in food, animal food, nutraceuticals and cosmetics.

In addition there is a potentially large market for natural antioxidants in the plastics

and biolubricants markets especially within food packaging and high value

pharmaceutical plastics for prosthetics.

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1. INTRODUCTION

This study is part of the ‘Rosemary Assessment of the Supply Chain (RADSC)’

project for Defra, which aims to provide convincing evidence that high value

specialised antioxidants from rosemary can be produced and extracted economically

in the UK overcoming any barriers to market uptake by the Food and Pharmaceutical

industries in the UK, Europe and Worldwide.

The study aims to identify the market for rosemary antioxidants and the principal

barriers to uptake in order to exploit previous R & D (RAPFI project) from the

Commercial Industrial Materials from Non Food Crops (CIMNFC) programme and

initiate robust marketing strategies and identify unique selling points.

The ‘Rosemary Antioxidants for the Pharmaceutical and Food Industries’ (RAPFI)

project set out to provide natural antioxidants for the Pharmaceutical and Food

industries from Rosemary crops grown in the UK. During the three years of the

project rosemary accessions were successfully selected with have high antioxidant

activity related to the concentration of carnosic acid. Three of the selected rosemary

accessions were planted in 2002 for field scale trials. Optimisations of the harvesting

of the crop for high levels of antioxidant activity were aided by the results of field

experiments. These showed that it may be possible to predict field, (drought, UV-B,

site and stress) and seasonal conditions likely to give the highest yields of

antioxidants. Results of field trials showed that rosemary crops grown in the UK

could provide higher levels of antioxidants than crops grown in more traditional areas

such as Spain and North Africa. This was because the antioxidant compounds are

used within the rosemary plant to prevent damage by free radicals cause by drought

stress, which is a condition not often, encountered for crops in the UK.

The project was also successful in developing a simple cheap process to maximize

levels of extracted antioxidants. Encouraging results showed that high concentrations

of antioxidants could be extracted efficiently from Rosemary using sonication to

enhance extraction from conventional solvents such as ethanol.

1.1. Rosemary

Rosemary (Rosmarinus officinalis L.) is a member of the Labiateae or mint family.

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It is a slow growing, cold sensitive, woody perennial cultivated for its aromatic

foliage. The crop is used in the UK primarily as a culinary herb with meats,

vegetables and in soups. Rosemary is widely grown on a commercial scale for its

high-value essential oils in Spain, France, Italy, Dalmatia, Tunisia and Morocco

(Upson, 1992; Svoboda and Deans, 1992). The majority of the oil consists of the

monoterpenes -pinene, camphene, -pinene, 1,8-cineole, camphor, bornyl acetate,

borneol and verbenone, which are present in all varieties, although there are

significant differences in the amounts of each compound between some varieties

(Upson, 1992, Cole 1999).

Rosemary (Rosmarinus officinalis, L.) has been recognised as a source of

antioxidants for a long time (Chipault et al., 1952). Plants need antioxidants in

order to protect their cells from destructive, oxygen species, the inevitable by-

products of photosynthesis (Knox and Dodge, 1985; Smirnoff, 1993; Foyer et al.,

1994; Asada, 1999). Reactive oxygen species can also be generated during the

hypersensitive response of plants to invasion by pathogens, physical damage,

changes in temperature, exposure to inorganic compounds, especially metals and to

UV radiation. As well as being potentially the greatest source of oxidants in plant

tissues, chloroplasts contain large amounts of the polyunsaturated fatty acid

linolenate in their thylakoid membranes, making them particularly susceptible to

oxidative damage. Because rosemary naturally grows in areas of drought and high

UV it has developed a natural protective system in the form of natural antioxidants

such as carnosic acid.

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1.2. Antioxidants

Antioxidants play a major part in ensuring that our foodstuffs keep their taste and

colour and remain edible over a longer period. Their use is particularly important for

avoiding oxidation of fats and fat-containing products. When antioxidants are

thoroughly mixed with fat or oil, the onset of the final stages of autoxidation, when

rancidity (development of unpleasant off-flavours and odours- becomes evident) are

delayed. Another important reason for the use of antioxidants is that certain vitamins

and various amino acids can easily be destroyed by exposure to air. They also help to

slow down the discoloration of fruit and vegetables. Ascorbic acid (vitamin C)

contained in many citrus fruits is a natural antioxidant and for this reason finds

frequent use in food production (E 300-E 304). Other natural antioxidants are

tocopherols (E 306-E309), which are members of the vitamin E family. Since both

compounds are very popular antioxidants they are also produced synthetically.

Permitted EU antioxidants also include the synthetic antioxidants such as gallates (E

310-E 312 and hindered phenols BHA (butylhydroxyanisol, E 320) and BHT

(butylhydroxytoluene, E 321).

Antioxidants listed for use in the EU:

E-Number Substance Some foodstuffs in which

they are used

E 300 Ascobic acid Soft drinks, jams,

condensed milk, sausageE 301 Sodium ascorbate

E 302 Calcium ascorbat

E 304 Ascorbyl palmitate Sausage, chicken broth

E 306-309 Tocopherols Vegetable oils

E 310 Propyll gallate Fats and oils for

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professional manufacture,

frying oils and fats,

seasoning, dehydrated

soups, chewing-gum

E 311 Octyl gallate

E 320 Butyl hydroxy anisol

(BHA)

Sweets, raisins, processed

cheese, peanut butter,

instant soupsE 321 Butyl hydroxy toluene

(BHT)

Controversy exists within the food antioxidant market; specific chemicals such as

BHT, BHA, sodium nitrate, and sodium nitrite have been implicated as causes of

cancer. These effects, have prompted concern from government and private agencies,

and provide areas of growth for natural antioxidants.

There have been two reviews of antioxidants used in industry recently which include

natural antioxidants:

Jones Michelle H (1998) C-020BN Antioxidants: A Market Overview. BCC report

Smith E., Crull A (2002) C-020BR Antioxidants: Markets, Materials, Trends. BCC

report

2. IMPORTANCE OF THE INDUSTRY

All lipids, including the esters of long chain fatty acids that make up 95% of oils and

fats, are subject to rancidity, a term derived from the Latin ‘rancidus’, meaning

‘stinking’ (Sanders, 1989). The prevention of rancidity is not merely of considerable

economic significance but essential to the wholesomeness and healthiness of food and

pharmaceutical products. The addition of antioxidants to foods not only is beneficial

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for health but also plays a role in preventing off flavour development, discolouration

and textural changes.

In addition to their uses in protecting food the human body also requires a supply of

antioxidants. The human body converts oxygen into energy and free radicals are

formed as natural by-products of this process, the overproduction of which can initiate

an oxidative chain process in the human body, which can in turn be responsible for

cancer, arteriosclerosis, infarction, allergies and other diseases (Yanishlieva and

Marinova, 1998). In addition to the free radicals produced by the body’s metabolism,

exposure to various environmental factors such as pollution, smoke and pesticides

cause damage to our cells as well. The level of intake of antioxidant nutrients

desirable for optimal nutrition is still an open question, and there is little information

on antioxidant bioavailability in vivo in humans. The relationship between antioxidant

status and intake is complex and are major targets of research. Although doubling

intakes of fruits and vegetables is likely to have important health benefits, the

European population remains reluctant to follow such advice. Barriers include

tradition, lack of and/or confused knowledge, and issues of availability, quality, cost

and convenience of fruits and vegetables. If people will not increase their

consumption of fruit and vegetables, supplementation or fortification can be

considered. Although antioxidants are ubiquitous in the plant kingdom, commercial

sources are limited and the suitability of an antioxidant for a particular application is

difficult to predict. Many links in the food chain could contribute to the optimization

of the antioxidant content of foods including plant breeding, agricultural practice,

harvesting practices, raw material selection, processing, storage, transport conditions

and cooking practices.

The global food preservative market at is at present suggested to be €422.7 billion,

reaching €522 billion by 2008 (Global Information).

2.1. The science of oxidation

Oxidative rancidity results predominantly from a series of reactions with oxygen,

collectively called ‘autoxidation’ (Hamilton, 1989). Autoxidation is a practically

irreversible free radical chain reaction. Free radicals have an unpaired electron, which

tries to find a match for by stealing an electron from something around it.

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Autoxidation is characterized by three stages, which are:

Initiation, during which free radicals are formed

Propagation, during which they are converted into other radicals

Termination, when these combine with one another to form stable products

During initiation and the early stage of propagation, oxidation proceeds relatively

slowly and at a uniform rate. It is only after this phase, called the Induction Period,

that off-flavours and odours begin to develop, as propagation chain reactions rapidly

accelerate the oxidation process. Lipid hydroperoxides are odourless and tasteless but

decompose readily, yielding lipid free radicals which catalyse further oxidation, as

well as relatively volatile compounds, including aldehydes, ketones and low

molecular weight fatty acids, that can impart off-flavours and odours at concentrations

as low as parts per million or per billion (Coppen, 1989). These volatiles, the final

products of rancidity, can be derived from any or all of the unsaturated fatty acids

originally present in the food, each of which can be oxidised through several different

mechanisms (Hudson, 1989).

Because of the different stages and complexity of autoxidation, it can be inhibited in

several ways, by different types of compound. The substances added to foodstuffs are

predominantly primary, chain-breaking phenolic antioxidants (Denisov &

Khudyakov, 1987, Gordon, 1990, Cuvelier et al., 1992, Yanishlieva and Marinova,

1998), although compounds from all these categories play a role in inhibiting lipid

oxidation, especially as synergists.

Whilst rosemary extracts may contain more than one category of antioxidant, most of

their activity has been attributed to phenolic compounds (Cuvelier et al., 1996;

Pearson et al., 1997), which can inhibit the propagation of oxidation by free radical

scavenging (Bolland and ten Have, 1947).

Oxidation temperature affects both reaction mechanism and antioxidant effectiveness;

the volatility of the antioxidant itself is also relevant, as it may have to survive quite

high temperature and pressures during production processes.

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Lipid oxidation, antioxidant action and antioxidant activity assays used with

rosemary extracts (adapted from Shahidi et al., 1992).

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Initiation

3O2

RH (lipid)

R• (lipid free radicals)

ROO•

ROOH (hydroperoxides)

Breakdown products:aldehydes, ketones,

alcohols, hydrocarbons, acids, epoxides

(including rancid off-flavour compounds)

Polymerisation products (dark colour, possibly toxic)

Changes of protein functionality & texture:

cross-linking, denaturation, insolubilisation, polypeptide

chain scission, enzyme inactivation & amino-acid

destruction

RH

R•

INITIATORSfree radicals

UV lightheat

enzymesmicroorganisms

metals/metalloproteins

etc

Oxidation of pigments, flavours & vitamins

TerminationOxidation

free radical scavenging

prevention of hydroperoxide

formation

prevention of hydroperoxide decomposition

Propagation

measured byDPPH• assay

measured byß-carotene,PV & AnV assays

measured byTBA-RS &

hexanal assays

2.2. Measurement of antioxidant activity

Methods of evaluating antioxidants depend on measuring their ability either to

scavenge free radicals, or to inhibit the oxidation of a lipid-rich substrate, i.e. to

increase its resistance to oxidative rancidity. The 2,2- diphenyl, 1-picrylhydrazyl

hydrate (DPPH•,) assay, which measures the neutralisation of the DPPH• radical

spectrophotometrically, is the preferred method of evaluating the free radical

scavenging activity of an antioxidant (Chen and Ho, 1997; Tagashira and Otake,

1998; Ibañez et al., 1999); it is simple, rapid and does not involve a lipid-rich

substrate. The -carotene assay is also a rapid and sensitive antioxidant assay, which

is not affected by coloured compounds in rosemary extracts (Svoboda and Deans,

1992). Whilst ‘true-to-life’ tests, over months of shelf storage, are conducted

occasionally for real food items, the onset of rancidity is usually accelerated using

heat. High temperature assays, such as the Rancimat method (100ºC–140ºC), have

been shown to predict less overall protection than that found at lower temperatures,

and the relative ranking of antioxidants can change with temperature. Simply put, “if

an oil tastes rancid, then it is rancid” (Rossell, 1989); sensory (organoleptic)

evaluation of the degree of oxidation in lipids or lipid-rich foods and pharmaceutical

substances, by properly trained taste panels, is recognised as the most reliable method

(Waltking and Goetz, 1983; Frankel, 1993, St. Angelo, 1996). However, many non-

subjective evaluations have been developed. Of these methods, the analysis by GC of

volatile products of lipid oxidation, collected from the headspace above the sample, is

the one that has been most thoroughly related to sensory evaluation (Snyder et al.,

1985;). Peroxide Values (PV), which measure hydroperoxide concentrations in lipids,

have shown strong correlations with flavour panel results. p-Anisidine Values (AnV),

measure the decomposition of some peroxides into aldehydes. They have not

correlated well with flavour panel responses for vegetable oils and milk fat, but highly

unsaturated oils can affect results, potentially invalidating the assay (Hudson, 1989).

The 2-Thiobarbituric Acid–Reactive Substances assay (TBA–RS) measures

concentrations of the oxidation product malondialdehyde and some other aldehydes,

but, for a range of vegetable oils and animal fats, values failed to correlate well with

flavour panel scores.

In the last few years, there has been a movement toward incorporating a further

measurement of antioxidant capacity. Oxygen Radical Absorbance Capacity (ORAC)

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was developed by the USDA to measure the antioxidant capacity of foods and

supplements (Cao, G., Alessio, H. and Cutler, R. G. 1993). The assay measures the

effectiveness of various natural antioxidants, present in the sample, in preventing the

loss in the fluorescence intensity of the fluorescent marker protein, -pycoerythrin

(beta-PE). Each reaction is calibrated using known standards of Trolox®, a water

soluble vitamin E analog.

3. BIOLOGICAL ANTIOXIDANTS

Fresh fruits and vegetables provide protection against the two biggest killers in the

Western lifestyle: cancer and cardio - cerebrovascular diseases. Their beneficial

effects have been attributed to various phytonutrients found in these foods including

natural antioxidants (Government recommedation: 5 portions of unskinned fresh fruit

and vegetables each day).

Activity Active compounds Fresh Sources

Antioxidants inhibit free

radical reactions and protect

cells from oxidative damage

such as alteration in the

structure and function of

cell membranes,

lipoproteins, carbohydrates,

RNA, and DNA

tocopherols

(Vitamin E)

ascorbic acid

(Vitamin C)

carotenoids

flavonoids

Spinach, asparagus, apples, carrots, celery,

nuts, seeds, whole grains

Both green and red peppers are a valuable

source of vitamin C

Tomatoes, peppers, carrots are good sources

of carotenoids.

Beetroot, carrots, herbs, tomatoes, red

peppers, and onions have high levels of

flavonoids

3.1. The search for new substances

Following consumer pressure and revised legislation, manufacturers are taking a look

at the natural antioxidant market. Commercial food additive suppliers now offer

antioxidant products derived from a variety of natural antioxidants. There is a range of

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formulations from fairly crude powders and oleoresins to extracts with certified

concentrations of specified compounds suitable for different application

According to Nutrition Business Journal (NBJ), San Diego, CA, the antioxidant

market, which includes vitamins A, C and E, rosemary, selenium, green tea extract,

grape seed extract, pine bark, CoQ10, bilberry, soy isoflavones, lutein, lycopene, and

olive leaf extract, grew by 1.5% in 2002, totalling approximately $2.5 billion in sales.

New research from Frost and Sullivan shows that from 2000 - 2009 the €15 million

total European antioxidant market (mostly synthetic) is set to grow by a mere 1.7%,

while over the same time frame, the natural antioxidants market will experience a

compound annual growth rate of 35%. Consumers are the ones really driving this

uptake. While no conclusive evidence has been forthcoming, there has been continued

debate over possible health risks involved in consumption certain synthetic

antioxidants. Any potential risks, proven or otherwise in food, drive demand for 'safe'

alternatives. As economic conditions return to a more healthy state and, as supply and

demand become more closely attuned, uptake of natural antioxidants is perceived as a

key growth area for the antioxidants sector as a whole.

To increase the scope for natural antioxidants, efforts are being made to obtain new

plant substances for the purpose. Up to now this has proved to be relatively difficult

because natural substances often possess other undesirable characteristics. Scientists

have found that a number of plant substances, such as those in rosemary and sage, are

effective antioxidants. However, there are two important aspects, which must always

be taken into account in food production. One is that naturally occurring substances

are not automatically safe for human health, and the other is that natural plant

substances often have a strong, distinctive, taste on their own. This is the reason why

newly discovered substances are not always used in food production and, in any case,

they would have to undergo a full safety evaluation as stipulated in the additives and

novel foods legislation. At present rosemary is not on the list of antioxidants

permitted by the EU. In April 2003 The Health and Consumer Protection

Directorate-General received a request from the European Rosemary Extract

Manufacturers Group to use rosemary extracts as an antioxidant in foodstuffs where

the rosemary extract could be optimised to enhance the antioxidative function and to

reduce that of flavouring. Such products would be considered as food additives and

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therefore require authorisation under Directive 95/2/EC. The Committee has been

asked to evaluate the safety of rosemary extracts as an antioxidant in foodstuffs. At

present European food producers, in the grip of a recession, are highly price sensitive

to the cost of all inputs. Suppliers can only utilise ingredients that offer a favourable

price/performance ratio in comparison with alternatives. As long as synthetic

antioxidant options are effective, low in price and still authorised for use, uptake of

naturals, in the present economic climate will be limited. However, chemical-derived

synthetic preservatives are viewed increasingly with some suspicion by consumers,

pushing food makers to source natural preservatives, such as rosemary extract,

instead. Last year, for example, Unilever-owned UK frozen food manufacturer Bird's

Eye announced a £4 million overhaul of its product range, removing all artificial

colourings, flavourings and preservatives from the products. Birds Eye beefburgers no

longer contain E621 and E223, otherwise known as the flavour enhancer monosodium

glutamate and the preservative, sodium metabisulphate. The two chemical additives

have been replaced by rosemary extract.

3.2. Rosemary antioxidants

Numerous phenolic antioxidants have been isolated and characterised from rosemary

leaves, including caffeic acid and its most active ester, or dimer, rosmarinic acid

(Cuvelier et al., 1996; Chen and Ho, 1997), which is an effective free-radical

scavenger (Chen and Ho, 1997). It is a relatively polar compound (Frankel et al.,

1996) and stable to heat (Richheimer et al., 1999).

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The most abundant phenolic compound in rosemary leaves is carnosic acid (Wenkert

et al., 1965; Brieskorn and Dömling, 1969), a labile abietane diterpene that undergoes

an oxidative degradation and rearrangement cascade, producing a series of

compounds, many with antioxidant activity (Richheimer et al., 1996, 1999), such as

carnosol, rosmanol (Schwartz and Ternes, 1992b), rosmariquinone (Hall et al., 1998)

and methyl carnosate (Cuvelier et al., 1994)

Carnosic acid is far less stable in aqueous media than in hot oil, where it is largely

converted to carnosol , which degrades in turn to rosmanol and other derivatives .

Rosmarinic acid, carnosic acid and carnosol are effective free radical scavengers and

prevent the decomposition of hydroperoxides (Chen and Ho, 1997; Hopia et al., 1996.

Carnosic acid is less polar than rosmarinic acid but significantly more polar than

carnosol. In emulsions, as predicted by the ‘polar paradox’, carnosic acid and

carnosol displayed greater activity than rosmarinic acid; however, in some emulsions,

carnosic acid showed far greater antioxidant activity than carnosol . Both compounds

demonstrated residual antioxidant activity after being completely consumed,

confirming that their breakdown products are also active antioxidants. The activity of

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carnosic acid has been shown to have approximately seven times the antioxidant

activity of BHT. Both carnosic acid and carnosol are good scavengers of peroxyl

radicals and carnosic acid is capable of neutralising hydrogen peroxide (Aruoma et

al., 1992). Rosmanol, a decomposition product of the breakdown of carnosic acid, has

been evaluated as approximately four times more active than synthetic antioxidants

such as BHT and BHA, in both lard and linoleic acid (Inatani, et al., 1983).

Rosmariquinone displayed antioxidant activity in soy-bean oil, stripped of

tocopherols, chlorophyll and carotenoids.

The antioxidant activity of the abietane diterpenes is attributed to the association of

the vicinal hydroxydes on the aromatic ring with the isopropyl group in the ortho-

position to them, whilst that of rosmarinic acid is attributed to the two sets of vicinal

phenolic hydroxides.

Rosemary contains two further abietane diterpenes; Ursolic and Oleanolic acid which

although not antioxidants their properties as good emulsifiers makes them important

in the cosmetic industry

3.3. Other natural antioxidants in use

3.3.1. Tocopherols (Vit E)Vitamin E is the generic term used for all of the compounds in this group. The

vitamin can exist as two types of structures: the tocopherol and tocotrienol

structures. There are many derivatives of these structures due to the different

substituents possible on the aromatic ring at positions 5, 6, 7, and 8.

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The tocotrienols share the same ring structure, but have an unsaturated tail.

Position of methyl groups on aromatic ring

Tocopherol structure Tocotrienol structure5,7,8 alpha-Tocopherol alpha-Tocotrienol

5,8 beta-Tocopherol beta-Tocotrienol

8 delta-Tocopherol delta-Tocotrienol7,8 tau-Tocopherol tau-Tocotrienol

Tocopherols (Vitamin E) are good antioxidants. They can interrupt free radical chain reactions by capturing the free radical. The free hydroxyl group on the

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aromatic ring is responsible for the antioxidant properties. The hydrogen from this group is donated to the free radical, resulting in a relatively stable free radical form of the vitamin.

3.3.2. CarotenoidsCarotenoids are natural pigments responsible for the bright colours of various

fruits and vegetables. There are many carotenoids in fruit and vegetables and

most have antioxidant activity. and ß-carotene and lycopene from tomatoes

have been the most studied. ß-carotene is composed of two molecules of

vitamin A (retinol) joined together. The antioxidant function of -carotene is

due to its unsaturation and thus its ability to quench singlet oxygen, scavenge

free radicals and protect the cell membrane lipids from the harmful effects of

oxidative degradation (Krinsky and Deneke, 1982; Santamaria et al. 1991).

The ability of beta-carotene and other carotenoids to quench excited oxygen,

however, is limited, because the carotenoid itself can be oxidized during the

process (autoxidation) (Burton and Ingold 1984; Cotgreave et al. 1988)

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3.3.3. Polyphenol/Flavanoid Flavonoids are naturally occurring polyphenols found not only in red wine but

also widely distributed in fruits (e.g., apples, grapes), vegetables (e.g., onions),

and in green and black teas. There are over 4,000 flavonoids of which about

260 are anthocyanins. Anthocyanins are natural pigments responsible for the

pink, scarlet, red, violet, and blue colours of flower petals, fruits, vegetables,

and other plant structures.

Flavonoids are typical phenolic compounds and act as free radical scavengers,

which makes them powerful chain-breaking antioxidants. Research on

flavonoids received an added impulse with the discovery of the French

paradox, i.e., the low cardiovascular mortality rate observed in Mediterranean

populations in association with red wine consumption and a high saturated fat

intake. The antioxidative effects of polyphenol compounds is due to their

chemical structures, the vicinal phenolic hydroxydes and their ability as

hydrogen donating free radical scavengers.

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Antioxidant Anthocyanin Flavaol/Flavone Catechin

R1 H or OH H or OH H,OH Glycosyl or

Gallate

R2 H or OH H or Glycosyl H or OH

R3 H or Glycosyl - -

R4 OH or Glycosyl - -

3.3.4. Carbohydrates and derivatives, ascorbic acidAscorbic acid and its sodium, potassium, and calcium salts are commonly

used as antioxidant food additives. These compounds are water-soluble and

thus cannot protect fats from oxidation: for this purpose, the fat-soluble esters

of ascorbic acid with long-chain fatty acids (ascorbyl palmitate or ascorbyl

stearate) can be used as food antioxidants.

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The relevant European food additive E numbers are: E300 ascorbic acid, E301

sodium ascorbate, E302 calcium ascorbate, E303 potassium ascorbate, E304

fatty acid esters of ascorbic acid (i) ascorbyl palmitate (ii) ascorbyl stearate.

3.3.5. Amino acid based substances, Glutathione (GSH) Mammalian cells have evolved numerous mechanisms to prevent or treat

injurious events that can result from normal oxidative by-products of cellular

metabolism. Glutathione (GSH) is a tripeptide, found in human cell tissue,

formed from the amino acids cysteine, glycine, and glutamic acid. As an

antioxidant, glutathione is essential for allowing white blood cells (or

lymphocytes) to express their full potential, without being hampered by

oxyradical accumulation during the oxygen requiring development of the

immune response. Interestingly, glutathione also acts to reconstitute vitamins

C and E after they have been oxidized, and therefore plays a determinant role

in their function.

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3.3.6. Minerals, seleniumSelenium is a trace element that is essential in small amounts, but can be toxic

in larger amounts. Humans and animals require selenium for the function of a

number of selenium-dependent enzymes, also known as selenoproteins.

Selenium has a variety of functions. The main one is its role as an antioxidant

in the enzyme selenium-glutathione-peroxidase. This enzyme neutralizes

hydrogen peroxide, which is produced by some cell processes and would

otherwise damage cell membranes.

4. CROP PRODUCTION AND RESEARCH Rosemary is widely grown in: Spain, Tunisia, Morocco, Turkey, France and Italy. In

Europe both fresh and dried rosemary are used for culinary purposes. Fresh crop is

exported from Spain, Israel, Columbia, Cyprus,

while dried rosemary is exported from Spain, and North Africa. The essential oil

from rosemary contains the monoterpenes: a-pinene, camphene, b-pinene, 1,8-cineole,

camphor, bornyl acetate, borneol and verbenone. Most essential oil is produced in

Spain and North Africa but this can have a high content of camphor.

22

Country Area rosemary

grown ha

Production method Uses

France 82 Cultivation Culinary

Essential oil

Germany 92 Cultivation Culinary

Extraction

Israel 53 Cultivation Fresh culinary 50ha

Extraction 3 ha

Italy 45 Cultivation

Morocco 12,000 Cultivation 2000ha

Wild harvesting 10,000ha

Dried

Essential oil (60

tonnes)

Spain Cultivation

Wild harvesting

Switzerland 0.5 Cultivation Fresh Culinary

Tunisia Wild harvesting Dried

Essential oil

Turkey 500-1000 Cultivation

Wild harvesting

450 tonnes dried

UK 20 Cultivation Fresh Culinary

(13ha)

Essential oil (2ha)

Antioxidants (5ha)

Canada Cultivation in trial plots

unlikely to overwinter

US Texas 200 Cultivation Extraction, dried

There is an increasing research interest and effort in the utilisation of rosemary crops.

23

4.1. UK

At present around 6228 ha of Medicinal and Aromatic Plants (MAP) crops are

produced in the UK (EUROPAM 2002) by field cultivation, mostly for culinary

purposes. A further area is cultivated under protection as pot herbs and under

hydroponics (Nutrient film technique NFT).

At present most rosemary is grown in the UK (13ha) for culinary purposes although a

small areas (2ha) is grown by Botanix for essential oil production. A further 5ha has

been planted since 2003 for antioxidant production following research on the

‘Rosemary Antioxidants for the Pharmaceutical and Food Industries (RAPFI) project.

This started in January 2000, as part of the CIMNFC programme, with the overall aim

to demonstrate the feasibility of growing rosemary in the UK to provide antioxidants

for the pharmaceutical and food industries. Research was undertaken at the National

Herb Centre and the Universities of Reading and Coventry aided by industrial

collaborators, J.K. Kings, Checkmate and Langford Electronics. Methods for

selecting high antioxidant rosemary were developed at the National Herb Centre l.

High producing accessions were selected with results indicating that rosemary crops

grown in the UK were capable of producing significantly higher levels of carnosic

acid than those grown in Spain and North Africa (Wellwood C.R.L. and Cole R.A.)

Unfortunately although UV radiation increased production of diterpenes the effect

was by no mean clear cut for carnosic acid and depended on the accession, which

made the development of a general predictive model difficult. However for those

24

rosemary accessions, which responded positively to UV radiation, one to three weeks

of high UV (i.e. sunny days in the UK) was likely to increase carnosic acid yield and

those accessions, which are affected positively by UV generally yielded high

concentrations of carnosic acid.

Research into increasing the concentration of antioxidant components showed that the

elicitors methyl jasmonate and Tween detergent reproducibly increased carnosic acid

concentrations in laboratory and field trials. However, it became apparent that water

availability and season were also important factors determining carnosic acid

concentration. There were consistent trends over two seasons with higher

concentrations of carnosic acid present during autumn to spring and lower

concentrations during the summer months. These results suggested that it was

possible to predict field and seasonal conditions likely to give the highest yields of

antioxidants.

In order for UK growers and companies to maximize benefits from the rosemary crop

it was important to value added by extracting rather than purely providing a crop into

a commodity market. Simple and economic extraction methods were required to do

this. At Coventry University methods of extraction were compared showing that

conventional solvents were shown to be more efficient than either CO2 or other novel

solvents systems and that sonication was a more effective extraction technique when

compared to thermal methods. With sonication ethanol, a poor thermal extraction

solvent but by far the least expensive solvent examined was as effective as other

solvents. Pilot scale extraction using ultra-sound was developed.

In order for food and pharmaceutical companies to have the confidence to extract and

use a plant based antioxidants the crop must be produced consistently from year to

year. A total audit trail for the production of antioxidants from rosemary crops was

developed identifying critical decision points during production and processing.

4.2. Spain

The production of MAP in Spain exceeds 14,000Mtonnes produced on 19,000 ha,

extensive amounts of which are wild harvested (716 ha are cultivated). Much of the

rosemary crop is wild harvested for drying or distillation but recent research on

drought stress (Munné Bosch, S. and Alegre,L., (2001), and subcellular

compartmentation of the diterpene carnosic acid and its derivatives in the leaves of

rosemary (Munné Bosch, S. and Alegre, L., 2001) have led to a better understanding

25

of the function of antioxidants in the rosemary plant and to the cultivation of rosemary

with irrigation.

4.3. France

In France > 33486 ha of MAP crops are produced. Perfume plants >25,000ha,

Lavandin 19,000 ha (2002),Lavender 5,000 ha; Medicinal plants 9,500 ha; Culinary

herbs 2,000ha; Over 40 ha of Rosemary are grown mostly for essential oil but the

majority of rosemary processed in France is imported from Morocco and Tunisia. In

1996 Cuvelier et. al determined the antioxidative activity and phenolic composition of

commercial extracts of sage and rosemary.

4.4. Germany

Germany is the leading country for import/export MAP in Europe. 25,994 ha of

herb crops are grown of which 92 ha are of rosemary. Research by Schwarz, K. and

Ternes, W (1992) determined the antioxidative constituents of Rosmarinus officinalis

and Salvia officinalis. Present crop research at the Federal Centre for Breeding

Research on Cultivated Plants- Quedlinburgfocuses on the selection of Origanum,

Salvia, and Thyme sp and Satureja hortensis (L) as natural antimicrobials and

antioxidants

4.5. Italy

In Italy 100 species of MAP are grown such as: bergamot (1357ha), peppermint

(239ha) ha), manna ash (200 ha), chamomile (171 ha), St. John‘s wort (156 ha),

liquorice (146 ha) and lavender (133 ha) (Survey on medicinal and aromatic plants in

Italy Carla Vender Istituto Sperimentale per l’Assestamento Forestale e per

l’Alpicoltura- ISAFA). 45 ha of rosemary are grown. Research on rosemary

production has focused on agronomy particularly to improve essential oil content. A

breeding program (1996-2000) at the University of Sassari in central-western Sardinia

(Prof Marco Milia and Prof Peter Deidda) set out to optimize biomass yield and

improve the quality of cultivated rosemary. Clones with higher leaf/wood ratio and

higher essential oil content were selected for the optimization of biomass yield. Weed

control is a serious problem in the cultivation of medicinal and aromatic plants

(MAPs). The aims of one project, in the Sacra Valley (north-western Italy) were to

verify the possibility of growing rosemary profitably. Different mulches were

compared against an unprotected control. Results showed that plants grown with

26

polyethylene and transpiring mulch increased canopy height and width more than

plants grown with the other treatments. Further research on propagation (Prof

Claudio Leto Dipartimento di Agronomia, Coltivazioni erbacee e Pedologia – ACEP

Palermo) and post harvest treatments (Prof Giuseppe Crivelli IVTPA - Ist. Sper.

Valorizzazione Tecnologica Prodotti Agricoli Milano)

are ongoing. Antioxidant

constituents of rosemary were identified by Bicchi et. al (2000)

4.6. Morocco

Rosemary grows wild on Morocco's sandy slopes and plains and Morocco exports 60

tonnes of its essential oil a year. To find ways of exploiting this resource rationally

and sustainably a company — Tafilalet Arômes Méditerranée (TAROMED) was

launched in 1999 by Dr Ismaili-Alaoui. Its first project focused on some10,000

hectares where the rosemary had never been exploited. Access roads have been built

through the rocky hillsides and water supply points provided. A distillation facility

was also set up, using results from an earlier IDRC-supported projects.

4.7. Tunisia

Rosemary grows wild in Tunisia and many of the low hills are covered with the

bushes, which may have been planted by the French about a hundred years ago.

The crop is hand harvested by local men from the villages and transported by donkey

to moveable stills. The rosemary could be harvested twice a year. Once one hillside is

harvested then the still is shifted to another one. By the time the other areas had been

harvested over a 3-month cycle the original plants have regrown and could be

harvested again. Then the whole area is left alone until the next year.

4.8. Israel

Recently, a novel method for producing antioxidants from Rosemary (Rosnox) was

developed in Israel by the Analit Extracts Company. In addition to the normal uses of

rosemary antioxidants it is also being used to prevent oxidation through assimilation

into a semipermeable wrapping.

Rosemary is generally grown in Israel in small fields of up to half a hectare per farmer

and is used only as fresh culinary herb. Producing enough raw materials for obtaining

the antioxidants required the development of a large-scale cultivation of Rosemary.

27

Rosemary accessions have been selected for the highest concentration of antioxidants,

approximately three times that of the standard lines and of imported Rosemary.

Further research has investigated the best harvest dates for achieving the maximum

yield of active materials and the effects of plant population and irrigation amounts on

yield. As in the UK research showed that the active components increased relative to

the amount of water applied but there was no effect of plant population on yield or on

active material concentration. An investigation into the importance of leaf age on the

concentration of active materials showed that as the harvest date was delayed, the

plants became woody and the leaf percent of total vegetative material decreased

which was different from the UK results where increasing age of the plants increased

the concentration of active components. This difference may be a result of

differences in the samples. But both research groups showed that the highest

concentration of active materials was in the higher and younger part of the plant.

Irrigation of Rosemary (500 mm/y plus rainfall) was necessary, in the geographic

region where the trial was conducted. The best harvest times were in early spring and

toward the end of the summer. The optimum plant population was shown to be

approximately 50,000 plants per ha, which from the results of the RADSC project

where plants had been planted at 30,000/ha. may prove a better density for

mechanical harvesting. In Israel field cost could be reduced by direct planting of

cuttings 10 to 15 cm long obtained from the top of the plant. Planting in this way into

a plastic mulch has been used successfully by Mike Brooke Organic Herb Trading

Company (pers comm).

4.9. Canada

Research by Norac Technologies Inc. has focused on fractional separation using

supercritical fluid carbon dioxide (Nguyen, et al.(1991 United States Patent

5,017,397 Process for extracting antioxidants from Labiatae herbs). In this

technique, the rosemary is supercritically extracted under relatively severe pressure

and temperature conditions to remove all oleoresin components quickly and

efficiently. The resulting supercritical fluid is then passed through a series of 2, 3 or

4 separator vessels in which the pressure/temperature conditions in each vessel are

set to selectively precipitate one of the oleoresin components of interest. This

technique offers considerable advantages in processing cost and in the utility of

some of the fractionated oleoresins obtained.

28

There is also research to evaluate rosemary as a potential medicinal plant for Alberta.

Norac Technologies, a division of Newlywed Foods in Edmonton, AB is currently

extracting antioxidants from leaves of imported rosemary, using a supercritical fluid

extraction method. Preliminary studies conducted at the Crop Divesification Centre

(CDCS) indicated that rosemary plants produced under field conditions are superior in

antioxidant content than imported rosemary. Norac Technologies, as an extractor, was

interested in using this high quality locally grown rosemary for their processing. This

required a detailed economic, risk, and logistic analysis of the cost and methods of

production and a screening of potential cultivars for foliage yield antioxidant content

and cold hardiness.

Field studies, in southern Alberta, to assess the possibilities of growing rosemary

cultivars (Arp, Barbeque, Majorca, Pink Majorca, Rex, Santa Barbara, Severn Seas,

Standard, Blue Lagoon, Primely Blue) as an annual crop under field conditions

showed some cultivars had greater productivity of phenolic compounds (phenolic

compound % x foliage dry matter yield). Rex produced the highest biomass (28.9 g

DW/plant). Experiments to evaluate the impact of freezing temperatures exposed in

the field, and killing frost on plant growth and antioxidant content in rosemary

showed that growth was arrested, in all these cultivars, by exposure to freezing

temperatures. Studies showed that 4 week old rooted stem cuttings can be used as a

planting material for field production of rosemary, whilst the highest leaf production

and antioxidant yield were observed from the plants grown at a spacing 30 cm x 20

cm at 50 N kg ha-1 and increasing N rates from 50 to 100 N kg ha-1 had no beneficial

effect on either leaf production or antioxidant production. This plant density is only

possible if growing rosemary as annual crop.

4.10. India

Rosemary is mostly cultivated as an irrigated and rain-fed crop in higher elevations.

In Tamil Nadu, rosemary cultivation is mostly confined to the high and middle

elevations of Nilgiris district. Research into high-yielding disease-resistant rosemary

varieties by scientists at the Horticultural Research Station of the Tamil Nadu

Agricultural University (TNAU led to the release of a new variety named `Rosemary-

Ooty (RM) 1'. The plants of this variety have vigorous growth with a mean plant

height of 62 cm and a yield potential of 12.40 tonnes of green leaf per hectare in a

29

year, which is 46 per cent higher than the local types. The first harvest of leaves

begins from 215 days after planting, and subsequent harvests can be done at an

interval of 3 to 4 months. Annually three to four harvests can be had, and this

perennial crop can be retained for up to twelve years. The new variety is resistant to

leaf blight disease caused by Rhizoctonia solani and it is also resistant to pests such as

whiteflies and aphids. Its leaves contained high rosemary oil (0.9 per cent). This

variety is suited for dry farming and it can be planted in June-July and September-

October at 50, 000 plugs/ha under rain-fed conditions. It is resistant to drought and

frost conditions.

5. DESCRIPTION OF THE ANTIOXIDANT INDUSTRY

The worldwide biological antioxidant market totals approximately $2.5 billion

(£1,750 million) in sales while the total European antioxidant market (synthetic and

natural) is worth 15 million euros (£10.5 million). Antioxidant sales increased by

23.7% in 2001 (Information resources Chicago). Market research indicated that there

is a demand for rosemary extract as an antioxidant and the present estimate of the

worldwide value of the market is between £70-90 million. This market would require

the production of 60,000 ha of rosemary assuming a price of £30/kg of 4% extract and

a content of carnosic acid of 50kg/ha. Rosemary antioxidants are produced by

companies in the US, Canada, mainland Europe and China.

Demand for antioxidants in the food industry are relatively stable while demand for

neutraceuticals and cosmeceuticals is expected to grow almost 10% yearly propelled

by new products offering benefits for an aging population and appearance-enhancing

applications. Through clinical research studies and efforts made to educate the public,

antioxidant ingredients are slowly becoming a common part of the dialogue

concerning health maintenance and promotion The scientific and academic

communities are consistently delivering the message that consumers need to eat a

minimum of five servings of fruits and vegetables a day to prevent disease. This is

not always possible and consumer interest in antioxidant preparations remains high.

For all markets the requirements for Rosemary antioxidants are similar Standardization of the product Minimal effect on taste or smell Environmentally friendly extraction (without the use of ozone producing solvents) Organic

30

Homegrown product (when targeting customers in the UK).

5.1. MARKETS BY PRODUCT TYPE

Antioxidants find applications in food, agricultural feeds, cosmetics, pharmaceuticals

and plastics. The types of antioxidants used in a particular market subsector are fairly

well-established. Restrictions in application are generally limited to cost,

effectiveness, stability within a given system, and the minimization of undesirable

effects such as discoloration in plastics. Additional regulations governing health and

safety exist within the food and agricultural markets and, to a lesser extent, in

cosmetics.

5.1.1. FoodAntioxidants are an increasingly important ingredient in food processing. Their

traditional role is, as their name suggests, in inhibiting the development of

oxidative rancidity in fat-based foods, particularly meat, dairy products and

fried foods. When antioxidants are thoroughly mixed with fat or oil, the

development of unpleasant off-flavours and odours is delayed. Antioxidants

play a major part in ensuring that foodstuffs keep their taste and colour and

remain edible over a longer period. Another important reason for the use of

antioxidants is that certain vitamins and various amino acids can easily be

destroyed by exposure to air, and antioxidants serve to protect them. They also

help to slow down the discoloration of fruit and vegetables.

However, more recent research has suggested a new role for antioxidants in

health care by inhibiting cardiovascular disease and cancer. Research has

shown that active life can be promoted by a diet high in natural antioxidants

from fruit, vegetables and red wine (in moderation). However there is a new

tendency to improve food raw materials by either traditional breeding, by

genetic modification, or by changing the feeding of animals. A second

generation of functional foods are being researched such as health improved

tomatoes or cereals with high contents of antioxidants, for example flavonoids,

carotenoids or tocopherols (vitamin E).

A further major trend in the food industry, driven by consumer concerns, has

been the shift from the use of synthetic to natural ingredients in food products.

31

While the growth in antioxidants in the overall food segment is relatively

small at 3.4 per cent in Europe there is predicted growth of natural

antioxidants from 18.2 per cent of the overall segment in 2003 to 27.0 per cent

in 2010. Fifty years ago, natural antioxidants were viewed as lacking in

potency when compared to the chemical blends. This may have been because

tocopherols are not very effective in vegetable oils, which already contain

significant amounts of tocopherols. The most successful combination in early

systems was BHA, propyl gallate and citric acid, all used to stabilize lard. It is

now recognized that since animal fats are deficient in tocopherols, addition of

tocopherols can significantly improve stability. Although the cheaper

chemical antioxidants still are preferred for many meat products a recent

European Fair research project (FFE 529/02/SME49) on Food and Health

protection found rosemary extracts (1000 ppm) protected such products

(meatballs, potato flakes and chicken meat) against oxidation better than

extracts from green tea, coffee, and grapeskin

The synthetic antioxidants BHA, BHT and TBHQ are still the major

antioxidants used to preserve vegetable oils for frying applications. While it is

important to achieve complete dispersion of the antioxidant in high fat

products, whether the antioxidant is natural or synthetic, adding small

quantities of antioxidants to food products that have small quantities of lipids

intensifies the need for dispersion. Timing is also important as during

processing, even a short delay before antioxidant protection is added can

reduce quality. To avoid delay in antioxidant activity, as many antioxidants

are not very soluble, antioxidant combinations are usually purchased in pre-

blended, pre-solubilized forms to facilitate ease of handling. Liquid forms

also provide a convenient application method for spraying on foods after

processing.

Food product developers have to deal with several different oxidation types.

Each type of food also poses a unique problem. In meat, for example, there is

deterioration of flavour during cooking or freezing, deterioration of colour

from oxidation of haemoglobin, and lipid oxidation of the fat portion. In baked

snacks with tiny amounts of fat, oxidation still can be an important factor in

32

staling. Grain flours contain fats in very low levels in the form of

phospholipids, however the problem is compounded by the large amount of

surface area that many snack foods present. Dry products have a porosity that

allows oxygen more exposure to the food. Vegetables might have oxidation

catalyzed by endogenous enzymes, and this cannot be prevented by the

addition of antioxidants. Enzyme inactivation by pH or heat is required to halt

these reactions. For natural antioxidant to penetrate the food product market

they need to be able to offer solutions to many different oxidation problems.

Two different antioxidants have often been found to be more effective in

complex food situations when they are used together, such as a blend of mixed

tocopherols and rosemary extract. One of the disadvantages of adding some

natural antioxidants such as tocopherol, polyphenols in fruit juices and plant

extracts is the problem of side reaction such as turbidity or sedimentation.

This difficulty can be overcome by the introduction a modified polysaccharide

matrix containing the antioxidant with a particle size in the range of 70-

200nm.

Among the spices and essential oils that have antioxidant activity, rosemary

extract has gained popularity as a ‘natural oxidation inhibitor’ in foods ranging

from McDonalds® chicken salad to health food bars. ‘Oxidation inhibitors’

are extracts or spices with antioxidant properties. These additives are

regulated, in the US and Europe, as flavours rather than as antioxidants

because they have sensory attributes that antioxidants do not possess.

However, the use of rosemary extract has been extended to applications in

confectionery and baked goods, and it is not uncommon for the usage level to

be so low that it is below the flavour threshold. In these applications the

sensory contribution is effectively negligible. Also, low-flavour systems, such

as standardized carnosic and rosmarinic acids, have been developed, which do

not contain the essentials oils responsible for the flavour. Although aromatic

rosemary extracts are fat-soluble the use of emulsifiers makes them dispersible

in hydrophilic food systems. The flavourings and drinks industry is a major

marketing opportunity for rosemary antioxidants with flavour removed.

Cadbury Schweppes, PepsiCo and Herblife already use Rosemary antioxidants

products in drinks, which would indicate that they have little impact on the

33

taste of the product. Animal and pet food is also a good potential market with

a number of companies already using it, notably Iams (owned by Proctor &

Gamble). The Pet Food Manufacturers Association stated that antioxidants are

becoming increasingly important in the products and given that the UK market

for pet-food was valued at £1.5 billion in 2000, this is a potentially large

market.

Many functional foods such as omega 3 and 6 fatty acids ( eicosapentanoic

acid EPA, docosahexanoic acid DHA and linoleic acid GLA) have rosemary

extract with tocoperol added to prevent oxidation of. These functional foods

can be stand alone products or for use in the fortification of a range of types

of foods, especially bakery products, dairy products, functional beverages,

sauces, nutrition bars, value-added seafood, margarines and spreads with DHA

and EPA.

5.1.2. Pharmaceuticals

In pharmaceutical terms antioxidants are used for two functions. Firstly, to

extend the self-life of medicines by retarding oxidation, secondly to combat the

damage caused by oxidative stress. Because the inclusion of antioxidants may

cause some toxic effects there are stringent rules on the use of antioxidants

included in medicine e.g. reason for inclusion, proof of efficacy, control in

production, labelling and safety information. Oxidative stress is the damage

done by "free radical" molecules, which are normal by-products of the body’s

oxygen consumption and metabolism. These free radicals are known to cause

damage to healthy cells and accelerate the aging process. Oxidative stress has

been linked to many age-related diseases and disorders such as cardiovascular

disease, cancer, diabetis and the formation of cataracts.

5.1.3. Nutraceuticals

34

The nutraceutical/dietary supplement (DS) industry is made up a diverse set of

products that are produced by a variety of manufacturers and distributed through

a variety of channels. For these reasons, characterizing the industry is difficult.

Herbals & Botanicals include products prepared by means other than extraction

(i.e., dried, crushed, and encapsulated); products that are extracts made from

any part of a plant and may include teas. The term herbal refers to the leaves

and stems of the plant while botanical refers to these parts in addition to roots,

seeds, and fruits. There is a grey area between the use of antioxidants in the

pharmaceutical and neutraceutical markets. In the nutraceutical market

antioxidants are also used to addresses a wide range of specific health issue such

as cancer prevention, cognitive function, eye health or immune function. This is

seen as a trend that has proliferated the antioxidant category. However rather

than provide a product with general antioxidant protection, the industry see it as

more beneficial to provide products, that incorporates various antioxidants and

other nutrients, targeted at a specific health benefit to consumers. Nutraceutical

manufacturers appear to be moving toward antioxidant blends that incorporate

both traditional vitamins and herbal extracts, rather than stand alone single

ingredient formulas, while food manufacturers continue to incorporate natural

antioxidants into traditional food formulations.

5.1.4. Cosmetics

The Egyptians were the first to recognise the health-giving properties of

cosmetics. A medical papyrus (Ebers) written in 1600 BC, makes frequent

reference to a number of cosmetic products. To many medieval Arab physicians

and their European counterparts, there were no distinctions between cosmetics,

fragrances and herbal medicines. The separation of the cosmetic and toiletries

industry from medicine and pharmacy was a 19th century phenomenon that

occurred when the modern pharmaceutical industry was first developed and

when the first government statutes regulating the sale of drugs were drafted. The

European cosmetics industry is frequently divided into the following sub-

sectors:

Skin Care, including sun care and other skin-care products;

Hair Care, including shampoos, conditioners and scalp-health products;

Body Care, including deodorants and a wide range of toiletries;

35

Decorative, including nail care, eye-care and colour cosmetics.

Interest in the health benefits of cosmetics was kindled by the development of

formulations to improve the appearance of sun (UV) damaged skin by the use of

antioxidants. The fastest-growing component of the cosmetics industry

(cosmeceuticals), with about 17% growth in both Europe and the US, has been

for skin care, with special emphasis on the sub-category of sun care and the EU

market is estimated at approximately $1.1 billion with the total market for

cosmeceuticals in Europe at approximately $1.5-$1.75 billion.

This cosmetic market is a further extensive market for rosemary antioxidants

particularly for skin rejuvenating and anti-ageing preparations. L’Oréal,

Christian Dior, Estée Lauder, Johnson & Johnson, Procter & Gamble,

Beiersdorf, BASF, Sheisedo and Avon Products all have significant lines of

cosmeceuticals with anti-ageing and sun care preparations dominating the

sector. L’Oréal has even established a joint venture with Nestlé—Inneov—

devoted exclusively to developing and marketing cosmeceutical products in

Europe. Smaller players, like Imedeen in the UK, Denmark-based Pharma nord,

Nu-skin, Indena and Weleda, the chemical firms Croda , who have backgrounds

in the natural body-care market, are also developing innovative cosmeceutical

lines. The cosmetics industry has been including herbs in cosmetics for a long

time but the marketing has changed to focus on the therapeutic effects of the

ingredients. While at present there might not be specific guidelines to deal with

cosmeceuticals, both the FDA and the EU are looking seriously at implementing

similar regulations to look at potency and efficacy. Much of the science is done

in-house so consumer confidence and a strong evidence base are tenuous and

lacking.

5.1.5. Plastics and Lubricants

Industrially, the applications of antioxidants are also numerous

Application Details

Elastomers Prevent oxidative deterioration from heat,

light and oxygen. Eases processing,

storage and increases quality of end

36

products.

Plastics Many plastics require stabilisation with

suitable antioxidants. Use and

materials define the amounts required

Diesel Unprotected diesel can discolour and

accumulate gum residues on storage,

reducing engine efficiency.

Lubricants Require stabilisation with

antioxidants to prolong/maintain efficacy.

Adhesives Provide stability, permanency and/or

minimal/no toxicity

.

Oxidation can weaken plastics, degrade oils, and destroy the integrity of

coatings. These chemical changes can eventually result in performance and

appearance changes in the material. Antioxidants are particularly important in

plastics, since most plastics undergo one or more high-temperature processing

steps, usually at the beginning of their life cycles. There are two basic types of

antioxidants used. Processing stabilizers are designed to help the plastic

survive the initial high-temperature processing step, whilst the other-

antioxidants prevent oxidation over the service life of the plastic.

In the coming decades renewable raw materials are expected to play an

enhanced contribution to the development of a sustainable society. With

regard to thermoplastic materials and lubricants, renewable raw materials not

only offer possibilities for the development of biodegradable materials, but

they can also function as additives and impart the desired properties in

synthetic thermoplastic materials and lubricants. The most researched natural

antioxidant for plastic material is -tocopherol, which is the most biologically

active form of vitamin E. There are three areas where natural antioxidants can

offer potential e.g. in food packaging, in high value pharmaceutical plastics

e.g. for prosthetics and in natural lubricants. One problem for any antioxidant

and particularly natural antioxidants used in plastics is to minimize any

37

discoloration in plastics caused by the antioxidant. This is not a problem for

rosemary antioxidants, where the pure compounds are pale cream in colour. A

more difficult problem would be to design an extraction procedure, which

produces sufficiently pure (> 90%) antioxidant at an economic price.

5.1.5.1. Elastomers (Chewing gum)Carnosic has been patented as an antioxidant stabilizer for chewing gum

Ford , et al. (2003) US Patent 6,670,437 Inventors: Ford; Barbara

Ann (Akron, OH); Hill; Valerie Anne (Akron, OH);Assignee: The

Goodyear Tire & Rubber Company (Akron, OH)

5.1.5.2. Food packaging

A major concern for synthetic antioxidants designed for food contact

materials is the problem of their migration into foodstuffs. Therefore, to

protect the consumer, the EFSA make an assessment of the potential

hazards from oral exposure to food contact material, which includes

plasticisers and colourants as well as antioxidants. To establish the safety

from ingestion of migrating substances, both the toxicological data and the

likely human exposure are combined. However exposure data is not

always easily available and it is assumed that a person may consume up to

1 kg of food in contact with relevant food contact materials.

Natural antioxidants are of high interest as stabilisers for such polymeric

materials and they have many advantages compared to synthetic ones.

They have excellent properties for use in stabilisation of food and drug

plastics, because the natural antioxidant and their oxidation products are

biologically degradable in nature and in vivo. Intensive research on the

stabilising properties of -tocopherol has been done during the last ten-

fifteen years. It has been found that in addition to its biological antioxidant

function, -tocopherol works well for process stabilisation. Material

stabilised with -tocopherol showed the highest stabilising effect

compared to the synthetic antioxidants but the stabilisation decreased

faster for the material with the natural antioxidant due to the higher

migration of -tocopherol.

38

5.1.5.3. Prosthetics

Since the 1960s ultrahigh molecular weight polyethylene (UHMWPE) has

been a primary bearing material in orthopaedic prostheses. Most

polyethylene components have been sterilized by exposure to radiation,

but in the presence of oxygen this promotes degradation and correlates

with component failure in the body. Stabilisation strategies of polymers

against oxidation are all based on reduction either of oxygen concentration

or radical concentration/reactivity. A wide selection of antioxidants able to

control radical reactivity are available on the market. Although the

addition of antioxidants is not yet permitted in medical purpose items, this

approach is now being investigated in order to improve the properties of

the polymer components. Natural antioxidants are likely candidates for use

in orthopaedic UHMWPE because they are obviously biocompatible and

are approved as antioxidant for food packaging.

5.1.5.4. BiodieselBiodiesels are monoalkyl esters derivatives of vegetable oils.

Environmental advance in their uses involve not only the fact that they are

renewable, but they provide enhanced lubricity, low exhaust emissions.

However biodiesel is susceptible to oxidation. Deterioration of various

biodiesels (e.e rapeseed, sunflower) have been reported (Propisil et al

2003). Oxidation stability is a key concern for vehicle and equipment

manufacturers, particularly fuel injection equipment manufacturers. There

is evidence from Germany, that poor quality control on B100 blends can

lead to plating the fuel injection equipment internals with oxide gums,

causing blockage and mal-operation.

5.1.5.5. Natural lubricants

Environmental acceptability and future availability, has driven research

into natural lubricants. Crop based lubricants based on vegetable oils are

now well established in environmentally sensitive areas from forestry and

agriculture to food and pharmaceutical processing. However most natural

lubricants still contain synthetic antioxidants highlighting the requirement

39

for further research on the potential for natural antioxidants in natural

lubricant.

6. COMPANIES INVOLVED IN THE EXTRACTION OF ROSEMARY

AND RELATED ANTIOXIDANTS

6.1. European companies

BFA laboratories (Bioprocess Fragrances Aromes) is specialized in the

production of raw materials for flavour and perfumery industries. BFA

Laboratoires were created in 1989, and focuses on distillation (Esterel) and

purification (BFA) of natural products. They have production plants in France,

Morocco and India. They produce a rosemary oleoresin, in Morocco, which is

sold as a rosemary antioxidant.

Contact details

BFA Laboratories, 107 Avenue Franklin Roosevelt, 06117 Le Cannet Codex,

France

Tel: 33(0)493699962

e-mail gry@bfa-lab.com

Chr. Hansen

The company develops natural ingredient solutions for the food, pharmaceutical,

nutritional and agricultural industries. The company is involved in the

development and manufacture of selected phytonutrients including natural

carotenoids (lipid soluble) and polyphenols and anthocyanins from both red and

white wine skins and seeds as a water soluble spray dried powder.

Contact detailsChr. Hansen, Bøge Allé 10-12, DK-2970 Hørsholm, DenmarkTel: +45 45747474

UK Contact details2 Tealgate, Charnham Park, Hungerford, Berkshire, RG17 0YT

Ciba Specialty Chemicals is a large- scale manufacturer of industrial

antioxidants used in the plastic additive industry. They have produced the first

40

natural antioxidant product, Ciba® IRGANOX® E 201, which is Vitamin E for

use in lubricants based on white oils for the food processing industry. The

product is FDA classified as Generally Recognised as Safe (GRAS) and

particularly recommended to protect base fluids during high temperature

procedures. The low volatility permits reduced antioxidant losses under high

temperature operating conditions and offers superior thermal stability over

conventional phenolic antioxidants such as BHT

Danisco is one of the world's largest producers of food ingredients. The company

develops and produces food ingredients, feed ingredients, sweeteners and sugar.

They produce two rosemary based antioxidants GRINDOX™ ( a mixture of

natural and synthetic antioxidants:-Ascorbyl Palmitate; Natural Mixed Tocophero;

Alpha Tocopherol; Rosemary Extract; Propyl Gallate; TBHQ; BHA; BHT;

Chelators) and GUARDIAN™ (Rosemary extract).

Danisco have recently produced a castor oil based plasticiser call ‘Grinsted soft-n-safe to replace phthalate plasticisers.

UK contactDanisco Cultor (UK) Ltd, Denington Rd., Wellingborough, Northants., NN8 2QJTel:

Bordas

The company has evolved from the cultivation, marketing and extraction of

aromatic plants to the manufacture of fruit derivatives and the synthesis of

chemicals for the fragrance, food and pharmaceutical industries. Bordas has

combined distilling and extracting natural essential oils (Citrus and turpentine) to

become one of Spain's largest industrial chemical producers. The company

produce the natural rosemary antioxidant BORDANTIX® which contains

Rosmarinic Acid, Carnosol, Rosmaridiphenol, Rosmaridiquinone, Carnosic Acid,

and Rosmanol. BORDANTIX® is advertised as having antioxidative activity

comparable to other synthetic and natural antioxidants available in the market.

Contact details

EVESA, Pol. Ind. De Camamento, P.O. Box 103, 11300 La Linea de la

Concepcion, Cadiz, Spain

Tel: 34 95669 9214/956698070

41

Email evesa@evesa.com

Grupo Natra

Laboratorios Natra, S.A.is a Spanish company created with the purpose of

extracting natural alkaloids from cocoa by-products. Nowadays, their activities

range from manufacturing natural extracts, natural and nutraceutical active

elements to food products. The group is divided into four business units of which

Natraceutical, S.A.is dedicated to the production of active principles and

nutraceuticals for the prevention of illness and for the food and pharma industry.

The company produces water-soluble dried extract: for the cosmetics,

pharmaceutical, food (dairy products, baby food.) and oil-soluble dried extract: for

the meat industry, oils, fried products. They produce AC-08 as a natural

antioxidant for the food industry, particularly the meat industry where the

rosemary flavour is appreciated. It is used extensively in the cosmetics industry as

a fragrance component and /or masking agent.

Contact details

Lourdes Roman, Natraceutical, S.A, Autovía A-3, Salida 343 (Camí de Torrent), 46930 Quart de Poblet (Valencia)Tel: + 34 961 920 851

Email: info@natraus.com

UK contact detailsNatraceutical UK, Lancaster Park, Newborough Rd., Needwood, Burton on Trent, Stafford, DE13 9DP Tel: 01283 575794

FLAVEX is a German company, which offers a range of rosemary products

produced by super critical CO2 extraction using ethanol as an entrainer. The

extracts contain 14-25% Diterpene Phenols (DTPs) of which carnosic acid is the

main constituent, with some carnosol its decomposition product. They also offer a

powdered rosemary leaf, which is high in rosmarinic acid and rosmanol.

Contact detail

Naturertrakte GmbH, Nordstrasse 7, D 66780 Rehlingen,

Tel: 49 68 35 91 950

Email info@flavex.com

42

UK Contact

Unit 1

Goose Foot Industrial Estate, Hereford, HR2 9HY

International Flavors & Fragrances is the worlds leading flavour and fragrance

company after aquiring Bush Boake Allen Inc. in 2000. Bush Boake Allen

supplies flavours and fragrances to the world's leading consumer products

companies for use in foods, beverages, soaps and detergents, cosmetics, toiletries,

personal care items and related products. Its aroma chemicals, natural extracts and

essential oils serve as raw materials for a wide range of compounded flavours and

fragrances. At present Bush Boake Allen do not produce their own rosemary

antioxidant extract but use Herbalox produced by Kalsec.

UK Contact details Roger Beckwith, Stafford Work, Long Melford, Sudbury, Suffolk,

CO10 7HU

Tel: 01787 314050

Jan Dekker BV

The company has two specialist divisions: Jan Dekker Cosmetic Ingredients and

Jan Dekker Food Ingredients. Dekker Food Ingredients specialises in custom

blending and marketing of antioxidants and has grown to become a European

market leader in the field of antioxidants and specialities. They make a range of

synthetic and natural antioxiodants based on mixed tocopherols such as PhytroX®

PTR D-mixed tocopherols, ascorbyl palmitate and rosemary extract based on a

starch carrier Phytrox Rosemary. They also produce a health food range

Nutroxi® which are flavonoid and carotenoid based based.

Contact details

Jan Dekker Nederland B.V., postal: P.O. Box 10, 1520 AA Wormerveer, The

Netherlands, visit: Plein 13 no. 1, 1521 AP Wormerveer, The Netherlands

Tel.: +31 75 647 99 99

43

Email: info@jandekker.com

UK Contact

David Prime, Jan Dekker (UK) Ltd. Food Division, Sunrise House, Hulley Road,

Macclesfield, Cheshire SK10 2LP, United Kingdom

Tel: +44 (0)1625 62 62 37, Fax: +44 (0)1625 62 62 38

E-mail: food@jandekker.com

Monteloeder.

Monteloeder supply lipid soluble Rosemary extract as Carnosic acid / Carnosol

(max. 40%) and a water soluble Rosmarinic acid (max. 10%). All extracts are

made with alcohol water.

Contact details:

C/ Miguel Servet 16, nave 17, (Parque industrial), 03203 Elche (Alicante) SPAIN, P.O. Box 580 Tel: +34 965 68 52 75 Email: mloeder@mloeder.com

Furesa (Natrafur/Furfurol) the company, which used to be called Furfurol and

is made up of Derivados Quimicos S.A. and Novochem. A multi-purpose plant

was officially opened on 14 May 2004 in Murcia (Spain) and is expected to be

operating under cGMP conditions later this year. It supplies fine chemicals and

active pharmaceutical ingredients (APIs) for both internal use by Bayer A G and

external customers.

They produce rosemary antioxidants as oil, water or glycol soluble extracts in

addition to dried powder for the food, cosmetic and nutraceutical industry

The rosemary extracts "CA": minimum 10%, 15%, 20%, 30%, 40% and 50% (dry

basis) is made up of the main phenolic diterpenes: carnosic acid, carnosol,

rosmarinic acid, rosmaridiphenol, rosmanol, epirosmanol, etc, and other phenolic

and flavonoid compounds as measured by hplc. The also produce a water-soluble

Rosemary extracts "RO" with minimum 8% rosmarinic acid (dry basis).

44

Contact details

FURESA - P.O. Box 18 - 30820. Murcia SPAIN.

Tel: 00 34 968 892855

Email: furesa@furesa.es

NATUREX manufactures and sells plant extracts for the food, flavour and

nutraceutical industries. The company offers plant extracts with flavouring,

colouring, antioxidant or nutraceutical properties. Morocco is the world's leading

producer of rosemary leaves and Naturex located a production unit fully dedicated

to the extraction of rosemary in this country. The company produce NAT’Stabil

Oxy’less. The rosemary extracts, Oxy’Less® products, were developed especially

to meet the requirements of the food industry. Naturex produce both refined and

unrefined rosemary extracts. Oxy'Less®.U (green powder, oil dispersible, pure

extract, light flavour): Oxy'Less®.UD (viscous green liquid, oil soluble, light

flavour): Oxy'Less®.UW (viscous green liquid, water dispersible, light flavor):

Oxy'Less®.CS (clear beige powder, oil dispersible, pure extract, very light

flavour): Oxy'Less®.Clear (amber liquid, oil soluble, water dispersible, very light

flavour): Oxy'Less®.Clear S (clear beige powder, oil dispersible, water

dispersible, very light flavour). Naturex sells Rosemary antioxidants as generally

accepted as safe (GRAS) and declared as natural flavour or herb extracts.

Naturex acquired Hauser/RFI’s rosemany extract business in March 2004. Hauser

has a long pedigree in extracting natural products for the health care industry. It

produced Taxol, an anti-cancer drug made from the bark of the Pacific yew tree

and predating that, the company manufactured Viadent, a toothpaste made from

an alkaloid of the bloodroot plant that has since been sold to Colgate. They

produce rosemary extracts StabilEnhance TM, WSR TM, OSR TM,

ColorEnhance TM). The drinks companies such as Snapple, Sobe and Hansen put

water-soluble rosemary StabilEnhance TM, in their beverages to keep that fruity

colour.

Jacques Dikansky, chief executive of France-based rosemary extracts firm

Naturex, believes that if the EU approves the labelling of the extracts as

45

antioxidants, the market has scope for even greater growth on a turnover of €34.8

million for 2004, a growth of 23.7 per cent on the previous year.

Contact details

Naturex, Jacques Dikansky, Chief Executive , Avignon, France

Nestle

Nestle has interests in rosemary antioxidants in a number of areas. The Nestle

Research Centre has researched the photoprotective potential of the dietary

antioxidants vitamin C, vitamin E, lycopene, beta-carotene, and the rosemary

polyphenol, carnosic acid as a suncare product. They are also marketing with

L’Oreal through the company Inneov anti-ageing and skin care products in

addition to nutritional supplements containing natural antioxidants. Within the

animal food sector Purina has been investigating the addition of rosemary extract

to low fat diets, which contain high concentrations of beneficial, easily oxidized,

unsaturated fats. Finally research at the Nestle Research Centre has shown that

ternary antioxidant vitamin mix consisting of ascorbic acid, a-tocopherol and

lecithin as well as a rosemary ext. with carnosic acid and carnosol as the two

major active ingredients exhibited strong antimutagenic activity .

Vitiva (Pinus TKI d.d.)

Vitiva is part of the Aktiva Group. The company built a new R&D and

production facility in Markovci near Ptuj in 2003. It is a dedicated facility in

which all the parts of the process (R&D, production, QC, storage) take place.

Research and production in Vitiva are entirely focused on natural substances.

Vitiva is ISO 9001 and GMP certified company supplying not only for food

industry but cosmetics and pharmaceuticals as well. Vitiva manufacture the ROS

range of product in Slovenia. They produces a broad range of rosemary extracts

available as oil soluble (to protect oils and fats) or water soluble (to protect water

soluble substances). The rosemary is solvent extracted and offered as

46

standardised rosemary extracts. The ROS products have high concentration of

active ingredients (20-40 % carnosic acid; 4% rosmarinic acid).

Vitiva claims to have a 70 per cent market share of the active ingredient market in Europe, though this figure is disputed by Naturex..

RAD Natural Technologies Ltd

RAD is a scientifically oriented Israeli company specializing in providing

solutions to oxidation problems in food, by using herbal extracts. They provide

extracts to the Food and Pet Food industries.

The OriganoxTM line of natural herbal extracts derived from Origanum vulgare,

with high, standardized antioxidant activity. OriganoxTM WS a water-soluble

extract in powder form a standardized for antioxidant activity, which contains at

least 22% of Total Phenolics, including 5%-10% of Rosmarinic acid and other

Hydroxycinnamic compounds and also in an oil dispersible OriganoxTM OS-A

Contact detail

RAD Natural Technologies Ltd., 6 Ravnitzki St., Petah Tikva 49277, Israel

Tel: 972 3 9049440

Email info@rad-int.com

RAPS GmbH & Co. KG

RAPS is a German manufacturer of spice extracts and seasonings with 12

subsidiaries and more than 30 distributors worldwide. RAPS supplies

manufacturers of the food and meat processing industries, catering, retail and

butcher shops. The company has a extensive knowledge of plant extraction and

mild processing of natural plant extracts using high pressure CO2 technology for

extraction. RAPS developed the natural antioxidants Stabiloton OS (phenolic

diterpenes content: 30% and WS base on rosmarinic acid.

Contact details

RAPS GmbH & Co KG, Adalbert-Raps-Str. 1, 95326 Kulmbach, Germany

Tel: 49 (0) 9221807248

e-mail export @raps.de

47

UK Contacct details

Ian Mackway

Tel 01280 705513

e-mail sales @raps.co.uk

Euro-Ingredients is a subsidiary of RAPS, which produces active plant

ingredient for the cosmetic and nutraceuticals industries. They benefit from RAPS

extraction expertise and the modern technological possibilities, supercritical CO2

and biofrost chilled grinding. They produce standardized and decolourised

extracts Rosemary Extract CA an oil-soluble extract with a high content of

carnosic acid (carnosic acid 40%), Rosemary Extract RA a water soluble extract

with a high content of Rosmarinic acid. Ursolic-/Oleanolic Acid Extract a high

content of ursolic acid beneficial for hair and skin by blocking elastase and

lipoxygenase enzymes.

Euroingredients sell their Rosemary Extract CA to the cosmetic industry to for

skin care and after sun products. The antioxidant activity of the rosemary extract

is used to provide protection against free radical activity (anti-ageing effect); as

well as stabilization of other valuable ingredients in oil soluble cosmetic

formulations and the reduction of lipid peroxidation in emulsions. They also

provide a Rosemary Extract RA, which is a water soluble extract with a high

content of rosmarinic acid. Due to this Rosemary Extract RA is a highly effective

natural antioxidant for aqueous cosmetic product.

Contact details

Euro Ingredients, Grobe reichenstrabe 27, D-20457, Hamburg

Tel: 40 (0) 1801188718

UK Contact Ian Mackway, RAPS (UK) Ltd, Ward Rd., Buckingham Industrial

Estate, Brackley, Northants, NN13 7LE

Tel: 01280 705513

e-mail sales@raps.co.uk

Provital SA. specializes in research, development, production, marketing and

distribution of natural active ingredients mainly of botanical origin. Since 1979

when the group's headquarters was founded in Barcelona (Spain), four subsidiary

48

companies are operating in Spain, France, Mexico and Poland. A wide product

range of natural and innovative ingredients is offered.

Contact details

Polígono Industrial Can Salvatella

Gorgs Lladó 200 - P.O.Box 78

Barberà del Vallès

Barcelona

Spain

E-08210

Tel: 0034 937192350

Fax: 0034 937190294

Email: marketing@provital.org

website http://www.provital.org

Symrise was formed by a combination of Haarmann & Reimer and

DRAGOCO manufacturers of fragrances and flavorings as well as raw materials

and active ingredients for cosmetics. They produce antioxidants for cosmetics as

active anti-aging ingredients from Dragosine, green tea concentrate and grape

seed extract. They also produce aqueous extracts such as CL extracts, which may

be an aqueous rosemary extract. In March 2005 they took over the English

company Flavours Direct

Contact details

Symrise GmbH & Co. KG

Mühlenfeldstrasse 1

37603 Holzminden

Germany

Phone +49 5531 90-0

UK contact details

Flavours Direct, Unit 10-12 Cockerell Road, Phoenix Parkway, Corby, Northants NN17 5DUTel:01536 408402Email us at lucyhall@flavours-direct.com

49

DSM Nutritional Products

In 2002 DSM acquired Roche’s Vitamins & Fine Chemicals Division in October

2003, which was subsequently renamed DSM Nutritional Products. DSM

Nutritional Products is a global supplier of vitamins, carotenoids (i.e. colorants

and antioxidants) and other biochemicals and fine chemicals to the food, feed,

health and cosmetics industries. It has eleven large production plants in seven

countries: Switzerland, France, Belgium, Germany, the UK, the USA and three

plants in China. Among the products successfully launched in 2003 were poly

unsaturated fatty acids (omega 3 fatty acids ) ROPUFA ‘30’ for the fortification

of a wide range of foods protected from oxidation by the natural antioxidants

tocopherol and rosemary. Further products containing natural antioxidants are

vitamin A in powder form for the cattle feed industry; pet foods based on

betacarotene and vitamin C; vitamin C applications for human use and new

ingredients for skin and hair care products.

Archer Daniels Midland Company (ADM)]

Archer Daniels Midland Company is one of the largest agricultural processors in

the world, they take crops and process them to make food ingredients, animal feed

ingredients, renewable fuels and naturally derived alternatives to industrial

chemicals. At present they do not appear to have any involvement with natural

antioxidants except Vitamin E but as these are used more by the Food industry it

would be surprising if they had no involvement.

6.2. North American Companies

Ecom

Ecom is an extractor of oleoresins and a supplier of ingredients such as natural

flavours, colours, and antioxidants. They produce a rosemary oleoresin NR3401,

which is sold to the food industry as an antioxidant.

80 Telson Road, Markham, Ontario, Canada L3R 1E5

tel 905 477 2441,

fax 905 477 2551

50

Hauser

In November 2004 Hauser sold its wholly owned subsidiary Botanicals

International Extracts to the Zuellig Group. Botanicals International Extracts is

the premier supplier of bulk natural ingredients to dietary supplement and food

ingredient suppliers in the United States. Naturex, a manufacturer of ingredients

for the food, flavor and nutraceutical industries, announced that it has acquired

Hauser/RFI’s rosemany extract business in March 2004.

BInutraceuticals

The company is owned by the Zuellig group, which offers a range of products

under different subsidiaries mainly to the pharmaceutical industry. BI

Nutraceuticals will be one of the first foreign botanical and extracts suppliers to

set up offices in China, an emerging market that offers both strong ingredient

sources and a fast-growing new nutraceuticals market. The Zuellig Group has

been present in China for more than 10 years, giving BI an important

infrastructure to leverage its growth there. BI Nutraceuticals manufactures,

markets, and sells a wide range of dietary supplement ingredient including:

standardized and ratio herbal extracts, whole herbal powders and herbal teas,

vitamins, minerals, spices, omega-3 fish oils, fruit and vegetable powders, and

other dietary supplement ingredients. RoseOx™ is the trademark of Hauser, Inc.

RoseOx® is a lipid soluble antioxidant made from rosemary extract containing

carnosic acid. Rossentia™ is a water soluble dietary supplement containing 4% or

9% super Rossentia, Rosmarinic acid.

Contact details

BI Nutraceuticals

2550 El Presidio Street

Long Beach, CA 90810-1193

Tel. (310) 669-2100

51

e-mail Customer Service manager twright@botanicals.com

Zuellig Group North America, Inc.

2550 El Presidio Street

Long Beach, CA 90810-1193

Tel. (310) 669-2100

Kalsec is an offshoot of commercial mint cultivation. They produce Herbalox®

seasoning a natural rosemary extract with standardized colour and flavour and

oxidation inhibiting properties. They produce W/HT-W compatibility with

aqueous solutions (e.g. marinades, brines, sauces), O/HT-O a concentrated, oil

soluble form, D-20 a dry product for better process compatibility, 25/HT-25 with

dispersibility over a large surface area without over mixing (e.g. ground turkey),

P/HT-P rapid aqueous dispersion in concentrated brines (e.g. pickle brines)

Contact details

Kalsec®, Inc. P.O. Box 50511 Kalamazoo, MI 49005-0511

Tel (269) 349-9711

Fax (269) 382-3060

info@kalsec.com

UK contact

Tel +44 (0) 1638 715011, Fax +44 (0) 1638 715031

ukinfo@kalsec.co.uk

Kemin

Kemin AgriFoods produces the Fortium® brand natural rosemary antioxidants for

the Food and Pet food industry. They produce Fortium R-WD a water dispersible

natural rosemary extract that can be formulated for use in marinades and brines

52

and injection technologies. For the pet food industry they produce the Naturox R

range of antioxidants containing mixed tocopherol, ascorbic acid and rosemary

extract. The rosemary extract is produced using the Advanced Phytonics

extraction process which utilises 1,1,1,2-tetrafluoroethane a highly selective, non-

toxic, pH neutral solvent and a liquid at low temperatures and pressures.

Contact details

Kemin Nutrisurance, Inc., 600 East Court Avenue, Suite 600-D., Des Moines, IA

50309 USA

Tel : 515.559.5100

Fax: 515.559.5259

email: Kemin Nutrisurance

Newly Weds Foods was started in1932 by Paul Angell and is a world leader in

food ingredient technology. Their rosemary extract is Supercritical Fluid CO 2

extracted by Norac

Norac Technologies is a division of Newlywed Foods in Edmonton Alberta,

Canada. They are a specialty chemical company producing ingredients to the

food, beverage, cosmetic, pharmaceutical and biotechnology industries. Norac

Technologies currently extracts antioxidants from leaves of imported rosemary,

using supercritical fluid extraction method. Preliminary studies conducted at the

Crop Diversification Centre (CDCS) in Canada indicated that rosemary plants

produced under field conditions are superior in antioxidant contents than that of

the imported rosemary. Norac Technologies is interested in using this high quality

locally grown rosemary for their processing. This will require a detailed

economic, risk, and logistic analysis of the cost and methods of production,

screening of potential cultivars for foliage yield and antioxidant content.

The produce Natureguard Rosemary extract-B a natural rosemary antioxidant in

oil-soluble, water-dispersible and powdered application formats for marketing by

Beta-Bioproducts into the cosmetic and personal care markets. They also produce

an oleoresin Labex in oil-soluble, water-dispersible and powdered application

formats

53

Contact details

James Zent

Newly Weds Foods Norac Division

Tel: 775 425-0492

RFI Ingredients based in Blauvelt, NY, is a manufacturer of natural ingredients

for the food, functional food and dietary supplement industries. The company,

which was formed in 1989, specializes in the supply of quality ingredients

(including certified-organic) and proprietary formulations designed in its in-house

applications laboratory. The company has manufacturing operations in North

America, South America and China. In addition to their international raw

materials sourcing platform, they also operate Atlantic Coast Functional Foods

(ACFF), a separate company that concentrates on selling functional foods into the

Asian market. The core product lines include: OxyPhyte natural antioxidants of

which Ultra Blend is a proprietary combination of white tea, rosemary, and apple.

Contact details

RFI Ingredients, 300 Corporate Drive, Suite 14, Blauvelt, NY 10913

Tel: 845-358-8600

Email: rfi@rfiingredients.com

Sabinsa Corporation manufactures and markets phytonutrients and standardized

herbal extracts, specialty, fine chemicals, and organic intermediates used in the

nutritional, pharmaceutical and food industries. The company also provides

custom manufacturing from lab scale to pilot / semi-commercial scale, and

process development. Sabinsa has a research and development facility near

Princeton, NJ and three manufacturing facilities in and around Bangalore , India.

Their Rosemary Extract - (Rosmarinus officinalis) is Standardized at 6%

Carnosic acid, 1.5% Ursolic Acid

Contact details

Sabinsa Corporation, 70 Ethel Road West, Suite 6, Piscataway, NJ 08854, USA

Tel:+1-732-777-1111

Email: info@sabinsa.com

54

55

 COMPANIES SUPPLYING ROSEMARY EXTRACT  COMPANY LOCATION

OF MAIN OPERATIONS

PRODUCT NAME LEVELS OF ACTIVE INGREDIENTS EXTRACTION PRICE

Sabinsa US not known Carnosic acid =6%, Rosmarinic acid = 1%, Ursolic acid =1.5%

Kemin US Fortium No trace of main active ingredients when tested

BINutraceuticalsUS RoseOxRossentia

Roseox 6% Carnosic acidRossentia 4% and 9% rosmarinic acid

Carnosic acid solvent acetoneRosemarinic acid solvent water

Roseox $93/kg without shippingRossentia $95/kgSuper Rossentia $130/kg

Kalsec US Herbalox Unknown $43/kg (£29.94)

BFA Labs. France Extrerel antioxidantSupraresin Carnosic acid Solvent

RAPS Ltd. Germany Stabiliton OS and WSCarnosic acid at least 17%.Testing showed 9.36% for OS and 2.07% for WS. 1.7%(OS) and 0.63% (WS) carnosol 0.09%(OS) and 0.044%(WS) rosmarinic acid.

CO2 extraction

Euro IngredientsGermany Rosemary extract CARosemary extract RA

40% carnosic acid 7.5% rosmarinic acid

Rosemary extract CA solvent extractionRosemary extract RA aqueous extraction

Carnosic acid £429.66/kgRosmarinic acid £123.82/kg

56

Monteloeder Spain

2 powder extracts available - Type A Carnosic acid (CA) and B Rosmarinic acid (RO)

Claim Carnosic acid is 20-30% in CA and 0.5% in RO. Carnosol 10-20% in CA and 0.5% in RO. Rosmarinic 0-1% in CA and 6-10% in RO. Rosmanol 0-5% in CA and 0.5% in RO

Alcohol/H2O

Carnosic acid 20% EUR 44/Kg (£27.89)Rosmarinic acid 6% EUR 26/KG (£16.47)

Naturex France NAT’Stabil Oxy’less. Stabilenhance oil soluble 5% carnosic acidStabilenhance water soluble 4-4.5% rosmarinic acidRosemary Oxyless CS

Stabilenhance oil soluble 55.6EUR/kgStabilenhance water soluble 61EUR/kgRosemary Oxyless CS113 EUR/kg

Furesa Spain Rosemary extract RO powder Rosmarinic acid = more than 6%

Bordas Spain Bordantix powder and liquid

Bordantix Powder C20 20% carnosic acidBordantix Powder A 5% carnosic acidBordantix Liquid C% 5% carnosic acid Claims carnosic acid levels of 14% in powder (we found 2.1% carnosic acid, 2.1% carnosol and 0.42% rosmarinic acid).

Bordantix Powder C20 @ EUR 135./kg.Bordantix Powder A @ EUR 18./kg.Bordantix Liquid C5 @ EUR 35./kg.

Extractos Natra Spain Unknown

Ecom Canada Rosemary NR3401 Unknown Distillation

Norac Canada Natureguard and Labex Unknown Supercritical CO2

Danisco Cultor Denmark GuardianGuardian 201 oil soluble 4% phenolic diterpenes (carnosic acid, carnosol)Guardian 2002 water soluble 4% phenolic diterpenes

CO2Guardian 201 £40/kgGuardian 2002 £40/kg

Symrise SwitzerlandRosemary CLhydrophilic rosemary herb distillate

Water/Distillation £11.45/kg

Vitiva (Pinus Slovenia ROS Unknown Acetonitrile/H2O/Alcohol 400EUR/kg (£253.33)

57

TKI)RAD natural technologies Israel Origanox Claim up to 50% Rosmarinic acid

58

7. EXTRACTIONConventionally phenolic diterpene rosemary antioxidants such as carnosic acid have

been extracted by solvents such as ethanol, acetone, acetonitrile whereas the

rosmarinic acid is usually extracted by water/ethanol mixtures. In the laboratory

acetone has been identified as a preferred extraction solvent, because of its selectivity

in extracting 90% or more of the carnosic acid from plant material and less of the

unwanted solids (Tena et al., 1997; Bailey et al., 1999; Bicchi et al., 2000). Acetone,

however, is not used on a large scale because of danger of explosion.

Various processes for obtaining antioxidant extracts from rosemary have been used.

The major problems to overcome are to obtain the extract with sufficient antioxidant

activity to allow usage at levels equivalent to the synthetic antioxidants (0.01-0.05%

of fat/oil) and to remove flavour, odour and colour components which may be

detectable in the treated food product at the usage levels required. The following

methods have been conventionally used to obtain antioxidant extracts from rosemary:

solvent extraction (polar and non-polar), aqueous alkaline extraction, extraction with

vegetable oils or mono- and diglycerides or both, steam distillation and molecular

distillation. These processes suffer from a number of disadvantages. The solvents

used are not effectively selective for the active antioxidant compounds, and

consequently, the resulting extracts are not as strong as the synthetic chemical

antioxidants. The solvents used include compounds such as hexane, acetone,

dichloromethane and ethanol, which can leave unwanted residues in the food products

and which in some instances are prohibited from use in food by regulation (ethanol is

the only solvent which is accepted by the food industry). Steam distillation removes

the essential oils but these are not responsible for the antioxidant properties of

rosemary. Processes using molecular distillation to concentrate the active fraction and

to remove colour, aroma and flavour components result in a different type of dilution

effect due to the presence of the distillation carrier which has a detrimental impact on

the solubility of the extract in fats and oils. Because of its ‘green image’ supercritical

CO2 is also used to extract antioxidants from rosemary.

Most of the rosemary antioxidants products discussed in section 6 have been extracted

by ethanol or CO2 extraction, although some distilled products are also sold as

antioxidants without much evidence that the volatile components have significant

59

antioxidant activity. Some cosmetic antioxidant products are produced by aqueous

extraction.

7.1. Conventional solvent

For solvent extraction the dried raw material is placed in the extractors, which are

made of stainless steel. The bed of material rests on a perforated false bottom. Solvent

is sprayed in at the top. It percolates down to the bed of material, carrying with it the

solubles, like volatile oils, fatty oils, colours, resins and pungent principles. The

contact time between solvent and raw material needs to be sufficient to ensure

diffusion and extraction of the constituents (3-4 volumes of solvent). Counter-current

extraction, where diluted extracts can be used for extracting fresh material can reduce

this volume. The more concentrated extracts leaving the columns are pooled and

distilled to remove the solvent. Vacuum is employed towards the end, to prevent

damage by heat and to ensure complete removal of solvents. Since food laws require

the oleoresin to contain not more than 30 parts per million of solvent residue, the final

traces of solvent have to be removed carefully. Ethanol is the solvent of choice for

extracting rosemary antioxidants because of its polarity and the permitted levels of

solvent in the extract and the potential environmental damage caused by the solvents.

Grinder

Extractor

Solvent

Solvent removal

Recycled solvent

Oleoresin

Rosemary

Solvent extract

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7.2. Supercritical CO2

Originally ground rosemary leaves were extracted with supercritical carbon dioxide at

a pressure of 300 bar and 35 .degree. C. only to remove the essential oil. The ground

leaf residue remaining after extraction was is then re-extracted with ethanol to obtain

an antioxidant fraction. More recently rosemary antioxidants have been extracted by

supercritical CO2 at higher pressures and the essential oils removed by fractionation.

Supercritial CO2 extraction theory

Supercritical or Liquid CO2 extraction operates under high-pressures, which

transforms carbon dioxide (normally a gas at atmospheric pressures) into a fluid with

enhanced solvent characteristics. Carbon dioxide has many advantages over other less

desirable organic solvents as CO2 is non-hazardous and leaves no undesirable solvent

residues. Low extraction temperatures preserve the integrity and quality of the

extracts and both the temperature and pressure of the extraction conditions can be

controlled for optimal results.

Under ambient conditions gases have no dissolving power, gases develop a dissolving

power only if, a particle density similar to liquids is created by applying pressure from

outside in the case of gases. A solvent’s capabilities in an extraction process depend

on the thermodynamic state of this solvent .

The vapour pressure curve ends in the so-called critical point where the vaporous and

liquid phases are identical. That means that one phase can no longer be distinguished

from the other. At temperatures and pressures above the critical point it is not possible

61

to reach the gaseous-liquid state again, either by reducing the temperature or the

pressure. In this homogeneous field the density and thus the dissolving power may be

altered continuously by variation of pressure and temperature. The separation of

components from plant material by means of a solvent under high pressure is a

stepwise process. The container is filled with the material to be processed and the lid

is closed. After the required pressure has been achieved, the solvent is passed through

the solid material until the desired result has been obtained. The separation of

components is only part of the separation; the solvent has to be separated from the

dissolved material. This separation is made with liquid solvents by means of

evaporation at increased temperatures; the level of solubility with compressed gases

can be obtained by either decreasing the density or the pressure and/or by increasing

the temperature. Extraction therefore consists of two steps, the extraction step and the

separation step. During the extraction step the soluble material is extracted with high

pressure from the solid matrix and transported away by the solvent; during the

separation step the dissolved material is removed from the solvent by decreasing the

solubilising power of the solvent and regenerating the solvent.

Pure liquid Carbon Dioxide is pressurized with a pump

The heater adjusts the temperature, Carbon Dioxide now supercritical

The extraction vessel is filled with raw material

Carbon Dioxide dissolves substances out of the raw material

Pressure drop caused through PCV 1 (pressure control valve)

Temperature adjustment with evaporator 1 st separation of extract (1st

fraction) and carbon dioxide/still solved material

Pressure drop through PCV 2

62

Temperature adjustment with evaporator 2

Separation of extract (2nd fraction) and clean gaseous Carbon Dioxide

Gaseous Carbon Dioxide is liquified in condensor and recirculated

Extracts is discharged periodically from DCV 1 and DCV 2 (discharge control

valve)

In the simplest case, an extraction unit consists of extractor and separator vessels

as well as of different heat exchangers, pumps, regulation valves and devices. The

extractor vessel is filled with the raw material, which is to be extracted. The

required pressure is achieved through CO2, which flows in from a tank. A high-

pressure pump is necessary to transport the solvent after the required extraction

pressure has been achieved. The pressure is maintained by an overflow valve,

which opens when the required pressure is exceeded and transports the enriched

solvent to the separator step. Usually, this separation step is connected with the

storage tank of the solvent. The pressure in the separator step and in the storage

tank will consequently be the same and will correspond to the saturation pressure

of the CO2 at the respective temperature. The decrease of density by means of

pressure reduction takes place directly in the valve. The separator vessel serves for

collecting and isolating the separated phases. The regenerated solvent is removed

at the top, transported to the pump and from there returned to the extractor vessel.

It might be necessary to repeat this procedure several times depending on the

extract quantity, the solubility of the extract in the solvent and the kind of

transition from the solid matter to the solvent. To improve efficiency extraction

vessels are usually connected in series with new raw material always in the last

vessel. In this stage the highest possible processing pressure, is used to extract all

constituents which are soluble under these conditions are collected in the separator

step. A further separation of the constituents is only possible by altering the

temperature or pressure. For example some extracted components are more

soluble in the CO2 and thus their at different temperatures will change the

concentration ratios. Fractionation can also achieved by variation of the dissolving

power of the solvent by changing the density Therefore, a separation of the

extractable proportions according to their solubility can be achieved by a repeated

extraction of the raw material with rising dissolving power due to increasing the

63

density. The most important factor in reducing solubility is the increasing

molecular weight of the individual components but other factors such as the

interaction of functional groups (free carboxylic acids, carboxylic acid ester,

amides, etc.) with the solvent determine the solubility.

Fractional separationNguyen et. al. have described procedures for the Fractional Separation of spices using extraction pressures in the range of 500 bar or higher and extraction temperatures of 80-100oC. Their data show that under such conditions the rate of extraction of oleoresin is approximately double the rate obtained at 300 bar and 60oC. These authors also show that under such extraction conditions, when also combined with a countercurrent cascading mode of extraction using four extraction vessels, the rate of oleoresin extraction is doubled again. Consequently the rate of oleoresin extraction under these conditions is four times that of traditional batch extraction at 300 bar and 60oC. Extraction costs are then close to a quarter of those obtained by the traditional method.

Fractionation of the very efficiently extracted oleoresins takes place simultaneously with extraction by passing the extract/fluid stream through a series of three or four separator vessels. Pressure and temperature conditions in each separator vessel are precisely chosen to precipitate a particular oleoresin component of interest. The last separator recovers the high quality essential oil. This system is demonstrated in Figure 2. The separator parameters shown are typical of those used, but are varied in each case to optimize the separation of targeted components for each specific raw material.

Fractional Extraction

Operation Pressure(bar)/Temp(oC) Product

Step 1 120/40 Volatile oil (Light fraction)

Step 2 300/60 Resin and vegetable oil (Middle fraction)

Step 3 >400/80 Heavy resin(Heavy fraction)

64

Fractional Separation

Operation Pressure(bar)/Temp(oC)

Product

Extraction 500/80 Total extract

Separator 1 250/65 Heavy fraction

Separator 2 120/60 Middle fraction

Separator 3 30/18 Light fraction

7.3. Mechanical extraction under pressure

Oleoresin can be obtained by pressing a mixture of ground dry rosemary leaves and

medium chain triglycerides (MCT). The mixture can then be subjected to gradually

increasing pressure from 50 bars to 100 – 250 bars. The oil contained 3-7% of

carnosic acid. but also volatile diterpenes.

7.4. Ultrasonic assisted solvent extraction

High frequency sound waves create compression and rarefaction zones within a liquid

medium. When the power exceeds a certain minimum value in the rarefaction zone,

the liquid molecules are pulled apart creating voids, bubbles, or cavitations filled with

gas or liquid vapours. After several acoustic cycles these bubbles suddenly collapse,

releasing into the liquid tremendous amounts of energy: around 5000ºC and 1000 bar

(~14,000 psi). The cavitational bubbles are the way through which the mechanical

energy of ultrasound is transformed and transferred into energy for use in the

extraction process. One of the best uses of ultrasound is to reduce the time to obtain

water/ethanol extracts. With ultrasound, cavitation bubbles collapse near plant cell

walls creating shock waves and liquid jets that cause the cells walls to break and

release their content into the solvent, speeding up and improving the diffusion process

65

that under normal solvent extraction conditions is very slow. The use of ultrasound

was demonstrated in the RAPFI project reducing the need for elevated temperatures in

the extraction particularly for poor thermal extraction solvents such as ethane.

7.5. Superheated water

Other ‘green extraction solvents such as super heated water have been used to extract

rosemary (Basile A., Jimenez-Carmona M.M., Clifford A.A., 1998).

7.6. Patents

A number of patents have been filed on the extraction of antioxidants from rosemary: Nakatani, et al. (1984) US Patent 4,450,097

Antioxidative compound, method of extracting same from rosemary, and use of same

Abstract

The invention provides a novel antioxidant obtained from rosemary and suitable for

preventing oxidation of various organic materials or, in particular, oleaginous

foodstuffs. The antioxidant is prepared by extracting rosemary with a non-polar

organic solvent and further extracting the thus extracted material with an aqueous

alkaline solution having a pH of at least 10.5 as a weakly acidic fraction soluble in

such a strongly alkaline solution. The extraction with the non-polar organic solvent is

preferably preceded or followed by steam distillation in order to remove any spicy

volatile materials undesirable when the antioxidant is added to foodstuffs or the like.

Column chromatographic separation of the above obtained weakly acidic fraction into

components gives a novel compound 7.beta.,11,12-trihydroxy-6,10-

(epoxymethano)abieta-8,11,13-trien-20-one as the effective ingredient of the

antioxidant prepared from rosemary. Characterization of the above novel compound is

given.

Inventors: Nakatani; Nobuji (Tokyo, JP); Inatani; Reiko (Osaka, JP); Konishi; Tadashi (Kanagawa, JP) Assignee: Lion Corporation (Tokyo, JP)

Nguyen, U., et al., (1991) US Patent 5,017,397,

Process for extracting antioxidants from Labiatae herbs

Abstract

Natural plant extracts exhibiting improved antioxidant properties are prepared from

ground leaves of the Labiatae family of domestic herbs by application of a

66

supercritical fluid extraction and fractionation process with carbon dioxide under

specific operating conditions. The extracts have greater antioxidant activity than

natural antioxidants extracted using other processes such as solvent extraction or

molecular distillation. The extracts of the invention are oil soluble, colorless and

flavorless when used at the optimum levels and provide more cost-effective protection

from oxidation than existing natural antioxidants. They are effectve in animal and

vegetable fats and oils, processed meats and fish, processed foods and beverages, food

colorants, cosmetics and health-care products at usage reates of 0.01-0.05% of fat/oil.

Starting materials include Rosmarinus spp. or Salvia spp. or Thymis spp. or Origanum

spp. of the common domestic herbs rosemary, sage, thyme and oregano or residues of

same after removal of volatile aromatic and flavor components by means of, steam

distillation, subcritical carbon dioxide or supercritical carbon dioxide at pressures of

less than 350 bar.

Inventors: Nguyen; Uy (4635 - 37 Avenue, Edmonton, Alberta, CA); Frakman;

Grigory (5504 - 179 Street, Edmonton, Alberta, CA); Evans; David A. (141 Tudor

Lane, Edmonton, Alberta, CA)

Nguyen, U., et al., (1992) US (1992) Patent 5,120,558

Todd Jr Paul H (US) (1991) US Patent 5061403

Abstract

A process of preparing an alkaline solution of Labiatae antioxidants essentially free of

lipids by agitating a solvent extract of the herb with an aqueous alkaline lower-

aliphatic alcoholic or polyol solution thereof, separating the aqueous phase from the

insoluble phase, and removing the alcohol from the aqueous phase by distillation to

give a stable product with an antioxidant strength of 0.2 or more, having a pH above

about 8.4, and having less than 75% water, preferably in the presence of a water-

immiscible solvent, and a stable aqueous antioxidant solution of a Labiatae extract,

consisting essentially of essentially all of the antioxidant substances present in the

herb, which is preferably rosemary, sage, or thyme, with an antioxidant strength of 0.2

or more, and less than about 75% water, preferably having a pH between about 8.4

and about 11.8, and therefore useful for a wide variety of antioxidant purposes,

including use in can liners and aqueous alkaline epoxy emulsions for preparing the

same, are disclosed.

67

Inventor: Todd Jr Paul H (US)

Applicant: Kalamazoo Holdings Inc (US)

Aeschbach , et al. (1993) US Patent 5,256,700Carnosic acid obtention and uses AbstractCarnosic acid is obtained by extracting sage and rosemary with an apolar solvent,

contacting the extract with an adsorbent material to separate carnosic acid from apolar

compounds of the extract, desorbing the adsorbent with a polar solvent and then

evaporating the solvent to obtain a residue containing carnosic acid. The carnosic acid

contained in the residue may be purified by crystallizing it from the residue.

Inventors: Aeschbach; Robert (Vevey, CH); Philippossian; Georges (Lausanne, CH) Assignee: Nestec S.A. (Vevey, CH)

Jianmin Jin (1995) CN1113514The process for preparing antioxidant from rosemary mainly includes such steps as

mixing rosemary with low-boiling-point organic solvent (such as acetone), thermal

reflux leaching, concentrating steam distillating dissolving with organic solvent (such

as alcohol), freezing, separating, filtering to obtain supernatant and precipitate,

concentrating and decolouring, and features that the active components of rosemary is

divided into supernatant and precipitate with respective purposes. Its advantages are

high yield rate and purity.

Inventor: Jianmin Jin (CN)Applicant: Jin Jianmin (CN)

Kahleyss Ralf et al (1995) US Patent 5433949AbstractIn order to produce natural antioxidants by extraction of spices selected from the

group of rosemary, thyme, sage and origano using compressed carbon dioxide and

oreganic solvents a) these spices are de-aromatized by extraction with carbon dioxide

at a pressure of 80 to 300 bar and at a temperature of 10 DEG to 80 DEG C., b) the

extraction residue obtained from step a) is treated with polar alcoholic solvents with 1

to 4 C atoms and/or non-polar hydrocarbons with 5 to 7 C atoms and c) the solvent

extract obtained from step b) is treated with active carbon and d) the extract obtained

from step c) is aftertreated with water at a temperature of 40 DEG to 100 DEG C. if

desired after extensively removing the solvent. Antioxidants obtained in this way are

68

almost completely neutral with regard to flavour, odor as well as colour and are more

effective than synthetic antioxidants.

Inventor: Kahleyss Ralf (De); Michlbauer FrApplicant: Sueddeutsche Kalkstickstoff (De)

Aeschbach , et al. (1998) US Patent 5,795,609Alkylene glycol extraction of antioxidants from vegetable matter AbstractAntioxidant substances are obtained from vegetable matter by mixing vegetable

matter containing antioxidant substances with a C.sub.2 -C.sub.6 alkylene glycol and

subjecting the mixture to pressure of at least 40 bar to obtain a liquid extract. In

carrying out the process, the vegetable matter mixed with the alkylene glycol has a

moisture content of from 5% to 30% by weight. Further, to subject the mixture to

pressure, the mixture is pressed, and additionally, the process includes filtering the

extract to obtain a clear extract.

Inventors: Aeschbach; Robert (Vevey, CH); Rossi; Patricia (La Tour-De-Peilz, CH) Assignee: Nestec S.A. (Vevey, CH)

Bailey ,   et al. (1999) US Patent 5,859,293High purity carnosic acid from rosemary and sage extracts by pH-controlled precipitation AbstractA process for the extraction and isolation of concentrated carnosic acid from plant

matter of the Labiatae family including contacting the plant matter with a water-

miscible solvent to form a plant extract and adjusting the pH of the plant extract to a

level between 7 and 10 while adding water in an amount sufficient to cause

precipitation of impurities while retaining the carnosic acid salt in solution. The

impurities are separated and the remaining aqueous solution is acidified to precipitate

a highly purified carnosic acid product which is essentially odorless, flavorless and

colorless.

Inventors: Bailey; David T. (Boulder, CO); Richheimer; Steven L. (Westminster, CO); Bank; Virginia R. (Boulder, CO); King; Benjamin T. (Boulder, CO) Assignee: Hauser, Inc. (Boulder, CO) Patent number: JP2000256345Publication date: 2000-09-19

Hasuda Ichiro et al (2000) Japanese Patent 2000256345Abstract

69

To inexpensively obtain the subject highly concentrated compounds in a simple

process by subjecting a plant material to a specific extraction treat ment. The

polyphenol compounds are obtained by the following process: a plant material is

subjected to extraction treatment with water at <=40 deg.C; thereafter, the resulting

extraction residues are subjected to extraction treatment with an aqueous alkaline

solution (e.g. a 0.05-5% aqueous solution of sodium hydroxide) at >=70 deg.C to

extract the objective polyphenol compounds, the extract aqueous solution mentioned

above is subjected to adsorbent treatment to adsorb the objective polyphenol

compounds alone, thereafter, both the treatment solutions afforded from the extraction

residues and the extract aqueous solution are then mixed together to obtain the

objective high-purity polyphenol compound in high yield, wherein the plant material

to be used is pref. at least one kind of plant selected from teas, cacao, rosemary, clove,

cinnamon, or the like. The polyphenol compounds thus obtained are usable as

ingredients for antioxidants, active oxygen scavengers, deodorizing agents, or the like,

through formulation.

Inventor: Hasuda Ichiro; Iwasaki Akira; Tawara HiroyukiApplicant: Hasegawa T Co Ltd

Ben-Yosef , et al. (2002) US Patent 6,335,373Process to produce stabilized carnosic acid in high concentration AbstractA novel process for the production of the natural antioxidant, carnosic acid, by

extracting it from rosemary leaves with an aqueous solution of a lower alkyl alcohol

in the presence of a water-soluble acid is described. The extraction of the carnosic

acid is very selective, i.e. very few other chemicals such as pro-oxidants from the

plant are extracted. Furthermore, a method for the stabilization of the extracted acid

from decomposition and a method of preparing the acid in high concentration are

described.

Inventors: Ben-Yosef; Gil (Even Yehuda, IL); Garbar; Arkady (Yokneam, IL) Assignee: Lycored Natural Products Industries, Ltd. (Beer Sheva, IL)

Reznik (2002) US Patent 6,383,543Process for the extraction of an organic salt from plants, the salt, and other similar salts AbstractThe invention relates to a completely water-soluble and long shelf-life antioxidant

material comprising sodium rosmarinate, which has been extracted from tissue of

plants of the Labiatae family without the necessity of adding extraneous sodium ions,

70

and aqueous solutions comprising the antioxidant material, to sodium rosmarinate

isolated from the extracted antioxidant material, to rosmarinic acid salts other than the

sodium salt, or admixtures thereof with the sodium salt, obtained by cation-exchange

with thus-isolated sodium rosmarinate, and to a process for preparing completely

water-soluble antioxidant material comprising the sodium salt of rosmarinic acid, and

its aqueous solutions.

Inventors: Reznik; Rena (Ra'anana, IL) Assignee: RAD Natural Technologies Ltd. (Petach Tikva, IL)

Bauman Davor et al (2004) Slovenian patent SI21460AbstractThe procedure comprises the following: a) grinding of dried plant material from the

mint family (Labiatae) in inert atmosphere; b) water or organic solvent extraction of

ground material obtained under a) and/or marc obtained after extraction of oil-soluble

antioxidants from plants of the mint family (Labiatae); c) evaporation of organic

solvent; d) concentration of the product obtained by traditional extraction, by ion

exchange chromatography; e) extraction of rosemary acid by liquid-liquid extraction;

f) concentration of product by elution chromatography; g) concentration of product

based on rosemary acid by application of high pressure gases, using a cosolvent

optionally. Products are applicable in antioxidative and antimicrobial agents.

Inventors Bauman Davor (Si); Hadolin Majda (Si); Kmet Matevz (Si); Rizner Hras

Andreja (Si); Knez Zeljko (Si)

Applicant: Pinus Tki D D (SI)

Haworth , et al. (2004) USPatent 6,824,789Method of extracting antioxidants from lamiaceae species and the extract products

thereof

Abstract

An increase in specific antioxidant activity of extracts from rosemary (Rosemarinus

officinalis) is obtained by the use of a blend of tetrafluoroethane and acetone in the

extraction process. A blend of tetrafluoroethane, acetone and methanol improves total

yield. A tetrafluoroethane and acetone blend has higher efficacy but comparatively

lower yields. The methods yield a liquid and oily extract that is readily mixed with a

liquid product such as soybean oil for addition to animal feeds and human food.

Inventors: Haworth; James (Des Moines, IA); Brinkhaus; Friedhelm (Des

Moines, IA); Greaves; John (Des Moines, IA)

71

Assignee: Kemin Industries, Inc. (Des Moines, IA)

Greaves , et al. (2005) US Patent 6,855,349

Method for simultaneous extraction of essential oils and antioxidants from Labiatae

species and the extract products thereof

Abstract

An increase in specific antioxidant activity of extracts from rosemary (Rosemarinus

officinalis) is obtained by the use of a blend of tetrafluoroethane and acetone in the

extraction process. A blend of tetrafluoroethane, acetone and methanol improves total

yield. A tetrafluoroethane and acetone blend has higher efficacy but comparatively

lower yields. The methods yield a liquid and oily antioxidant extract that is readily

mixed with a liquid product such as soybean oil for addition to animal feeds and

human food. The methods simultaneously yield pharmaceutical grade essential oils in

high yields.

Inventors: Greaves; John A. (Ankeny, IA); Brinkhaus; Friedhelm (Urbandale,

IA); Haworth; James E. (Des Moines, IA)

Assignee: Kemin Industries, Inc. (Des Moines, IA)

8. REGULATION AND LEGISLATIONRosemary antioxidants have potential markets in Food, Animal Food, Nutritional

Supplements, Traditional Herbal Medicines and Cosmetics. The regulations and

legislation for their use are very different for each different market and in addition

regulation and legislation is different between Europe and the US.

8.1. Foods

8.1.1. European Food Safety Authority (EFSA)

EFSA is the keystone of European Union (EU) risk assessment regarding food

and feed safety. The EFSA provides independent scientific advice on all

matters linked to food and feed safety - including animal health and welfare and

plant protection - and provides scientific advice on nutrition in relation to

Community legislation. EFSA’s risk assessments provide the European

Commission, with a scientific basis for defining legislative or regulatory

measures required to ensure consumer protection with regards to food safety.

72

Antioxidants are subject, just like any other food additive, to stringent EU

legislation governing authorisation, use and labelling. Under Directive 95/2/EC

on Food Additives other than Colours and Sweeteners legislation says

antioxidant additives must be to be declared on food packaging by their

category (antioxidant, preservative, colour, etc) with either their name or E-

number on ingredient labels of all foods that contain them.

8.1.2. Food and Drug Administration (FDA)

FDA is responsible for protecting public health in the US by assuring the safety,

efficacy, and security of human and veterinary drugs, biological products,

medical devices, the food supply, cosmetics, and products that emit radiation.

American (FDA) law requires a food manufacturer to get approval before using

a new additive, or before using a previously approved additive in a new way or

in a different amount. In its petition for approval, the manufacturer must

demonstrate that the additive is safe for consumers, considering: the probable

amount of the additive that will be consumed with the food product, or the

amount of any substance formed in or on the food resulting from use of the

additive; the cumulative effect of the additive in the diet; the potential toxicity

(including cancer-causing) of the additive when ingested by humans or animals.

The food additive regulations require the additive to be of food grade and be

prepared and handled as a food ingredient. Also, the quantity added to food

must not exceed the amount needed to achieve the manufacturer's intended

effect.

8.2. Rosemary and other natural antioxidants

Although antioxidant additives are a problem for the food industry leading to attempts

to find naturally occurring substitutes for synthetic antioxidants. Both European and

American law requires that newly identified natural antioxidants, like other new food

additives, must undergo rigorous toxicological tests before they can be approved.

The perceived barrier to the uptake of rosemary antioxidants in Europe is that it is not

on the EC positive list of approved additives. In April 2003 The Health and

Consumer Protection Directorate-General received a request from the European

Rosemary Extract Manufacturers Group to use rosemary extracts as an antioxidant in

foodstuffs. In cases where the processing of the rosemary extract could be optimised

73

to enhance the antioxidative function and to reduce that of flavouring these products

would be considered as food additives and therefore require authorisation under

Directive 95/2/EC. The European Food Safety Authority (EFSA) has been asked to

evaluate the safety of rosemary extracts as an antioxidant in foodstuffs. EFSA has

requested further toxicological and dietary exposure assessment in order to do a risk

assessment. The following companies, Robertet, Naturex, RAPS, Danisco, Natrafur

(Furfural), Bordas and Nestle have contracted CANTOX consultants in human health,

toxicology and regulatory affairs to provide this toxicological data.

(contact Nigel Baldwin The Science & Technology Centre, University of Reading,

Earley GateWhiteknights Road, Reading RG6 6BZ, UK

Tel: +44 (0)118 935 7162).

Up to date Cantox have found no toxicological problems in the traditional usage of

rosemary with traditional usage of rosemary up to 7gms of dried rosemary. The only

potential problem has been to show the safety of the average daily intake ADI,

equating to 1.8gm dried rosemary, if rosemary antioxidant is added to food as an

additive. One of the greatest difficulties in submitting to EFSA has been the widely

different antioxidant products produced. The carnosic acid/carnosol/1.8 cineol ratio

will probably be used as a defining criterion in the use of rosemary antioxidant as a

flavouring or as an antioxidant. This is because 1.8 cineol, a major component of

rosemary essential oil, was evaluated, as component of natural sources of flavourings,

by the Committee of Experts on Flavouring Substances of the Council of Europe

(CEFS), resulting in the allocation of a provisional TDI of 0.2 mg/kg bw. This TDI

was derived from a minimum lethal dose of 60 mg/kg bw for children applying a

safety factor of 300 (Council of Europe, 2000). Data from new studies on the use of

rosemary was submitted at the end of October. Rosemary extract sector awaits EFSA

approval to label the ingredient as an antioxidants probably in 2006.

The status of rosemary extracts containing carnosic acid/carnosol as an additive will

not reflect on the status of the other major antioxidant in rosemary extracts,

rosmarinic acid.

The FDA requires ingredients such as herbs and other novel ingredients, when added

to conventional foods, should either be pre-approved as a food additive or,

alternatively, meet the requirements of the "Generally Recognized as Safe" (or

GRAS) provisions. At present most natural antioxidant are considered GRAS if the

quantity of the substance added ( 0.5g dried) to food does not exceed the amount

74

reasonably required to accomplish its intended physical, nutritional, or other technical

effect in food; the quantity of a substance that becomes a component of a food as a

result of its use in the manufacturing is reduced to the extent reasonably possible; and

the substance is of appropriate grade and is prepared and handled as a food ingredient.

Under FDA regulations rosemary spice or oleoresin is considered GRAS (generally

recognised as safe) and has the food labelling code SP/ESO, GRAS 182.10, 182,20.

8.3. Nutritional supplements and Herbal Medicine

In the US, UK and Netherlands legislation on Nutritional supplements and Herbal

medicines has been very different from the rest of Europe. Recent Directives from

the EU (EU Food Supplements Directive and the Traditional Herbal Medicines

Directive) have been aimed both to clarify and to unify the legislation in these areas

8.3.1. EU Food Supplements Directive

This directive was agreed in Brussels and published in the Official Journal in

May 2002. It created a single market in food supplements throughout the

European Union by harmonising the regulation of such products. It determines

what ingredients may be used and at what levels they may be present. It also

regulates supplement labelling and marketing. In the first instance, the Directive

deals only with vitamins and minerals, but it contains provision for extension to

other ingredient categories, such as herbs in the future. Those elements of the

Directive which deal with the ingredients that may be used in supplements and

the labelling of products were turned into national legislation by the Food

Supplements (England) Regulations 2003 and similar measures for Scotland and

Wales. The Directive and the national regulations list those nutrients and

nutrient sources that may be used. Substances not on the list of approved

nutrients and nutrient sources may not be used after July 2005 (and even then

only until 2009) only if a full scientific dossier has been compiled and submitted

for consideration by the European Food Safety Authority (EFSA) prior to July

2005, and provided that EFSA has not decided that the substances is unsafe.

8.3.2. EC Traditional Herbal Medicines Directive 2001/83/EC

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This directive prescribes that no medical product may be placed on the market

without obtaining marketing authorisation. This requires submission of tests on

quality, safety and efficacy of the product. Because these tests and trials for

many of the small or medium sized companies involved with the production of

medicines derived from herbs and nutraceuticals would be a significant

financial burden the EC has reached a compromise. With respect to the UK

where a herbal material had been previously licensed as a medicine, is on the

Medical Control Agency's (MCA) general sales list and had a long, documented

history of use, (30 years use in the UK or 15 years in the UK and 15 years in

abroad) it would be considered a 'traditional medicine' and the regulatory

requirements would be fairly straightforward. There would be no requirement

for efficacy trials, except from the literature, but support would be sought from

experts in the field and medicinal herbalist for the registration of products. Full

traceability, Good Agricultural Practice (GAP) and Good Manufacturing

Practice (GMP) would be required for the production

8.3.3. Dietary Supplement Health and Education Act (DSHEA1994)

In the US defines dietary supplements as (A) a vitamin; (B) a mineral; (C) an

herb or other botanical; (D) an amino acid; (E) a dietary substance for use by

man to supplement the diet by increasing the total dietary intake; or (F) a

concentrate, metabolite, constituent, extract, or combination of any ingredient

described in clause (A), (B), (C), or (E). The law clarifies that a dietary

supplement is not a drug or food additive, and sets forth guidelines for the

dissemination of truthful information about the supplements effect on "body

function" on package labelling. FDA regulates dietary supplements under a

different set of regulations than those covering "conventional" foods and drug

products (prescription and Over-the-Counter). Under the DSHEA, the dietary

supplement manufacturer is responsible for ensuring that a dietary supplement

is safe before it is marketed. FDA is responsible for taking action against any

unsafe dietary supplement product after it reaches the market. Generally,

manufacturers do not need to register their products with FDA nor get FDA

approval before producing or selling dietary supplements. Manufacturers must

make sure that product label information is truthful and not misleading. FDA's

post-marketing responsibilities include monitoring safety, e.g. voluntary dietary

76

supplement adverse event reporting, and product information, such as labelling,

claims, package inserts, and accompanying literature. The Federal Trade

Commission regulates dietary supplement advertising. FDA regulations prevent

statements that these products are intended to diagnose, treat, cure, or prevent

disease.

8.4. Animal Feed

Regulation 178/2002/EC: established general principles and requirements of food law

and procedures in matters of food safety for animal feed. Directives 70/524/EC and

87/153/EC cover additives and guidelines for their assessment additives in animal

feeding-stuffs. The newly established EFSA has scientific panels on Additives and

Products or Substances Used in Animal Feed).

In the US any substance intentionally added to an animal feed, including pet food,

must be used in accordance with a food additive regulation unless it is generally

recognized as safe (GRAS) among qualified experts for its intended use. The

manufacturer must show that the food additive is safe for its intended use, under the

conditions of use specified.

8.5. Cosmetics Products

77

The Cosmetic Products (Safety) Regulations 2004 are based on the EU Cosmetics

Directive EU Cosmetics Directive (76/768/EEC) and its amendments. Cosmetic

products are required to meet various safety requirements but, unlike medicinal

products, they do not require a licence and they are not required to demonstrate

efficacy. The Directive sought to place the onus on manufacturers and suppliers to

ensure a cosmetic product put on the market within the Community must not cause

damage to human health when applied under normal conditions

In the US the Food, Drug, and Cosmetic Act requires that cosmetics and their

individual ingredients must be safe and that labelling must be truthful and not

misleading. The Food and Drug Administration’s (FDA) legal authority over

cosmetics is comparable with its authority over other FDA-regulated products. The

Cosmetic Ingredient Review (CIR) reviews the existing literature on ingredients and

makes recommendations to the industry however there is nothing that requires any

member company to respond to the board's safety or health recommendations.

9. THREATS TO UK AND EUROPEAN PRODUCTION

9.1. Low cost producers

According to American Spice Trade Association (ASTA) rosemary is considered one

of the largest volume basic extractives (the others being anise, cinnamon, cloves,

mint, nutmeg, and thyme). Many companies world wide are supplying dried

rosemary and rosemary essential oil but a significant number are now also providing

a SFE-CO2 rosemary extract.

9.1.1. ChinaChina introduced rosemary as a crop in 1981. It is grown in Guizhou, Hunan

and Yunnan provinces and on Hainan island

78

Guangzhou Honsea Sunshine Bio-Science & Technology Co., Ltd.] is a high-

tech enterprise integrated with R & D, manufacturing and marketing which

located in Guangzhou China. They have established extraction facilities in

Yunnan provinces working to GMP standards. They use SFE-CO2 to supply

natural herbal extracts and essential oils for health functional food, herbal

medicine, aromatherapy & cosmetics. The corporation is engaged in planting,

producing, reseaching and developing a series of rosemary products.

Rosemary should grow in Yunnan's climate, which is characterized by small

seasonal change in temperature, but great difference in daytime temperature,

and distinct contrast between dry and wet seasons. Its mean annual

temperature increases from 7ºC in the northwest to 22ºC or more in the

Yuanjiang River valley. It has abundant rainfall and a mean annual

precipitation of 750-1,750 mm. The rainfall in the wet season of May to

October accounts for 83 per cent of the annual precipitation.

79

Hainan Super Biotech Co Ltd

With scientific research over the past 3 years the Hainan Super Biotech

Co,.Ltd has successfully established rosemary plants in Guizhou, Hunan

provinces and on Hainan island . The climate in these provinces should grow

rosemary successfully as they have relatively warm winter temperatures and

plentiful rainfall during the summer months although the hot wet summers

may make diseases more common. The company has joint ventures with the

local farmers offering technical guidance.

The main product of the company is rosemary extract, which is exported to

Europe, Americas, Japan and Korea. They also produce for the domestic food

market. They produce solvent extracted carnosic acid >20% (RM-A62),

≥15% (RM-A41),>5% (RM-A) >20%, rosemarinic acid (RM-W21) and a

SFE-CO2 extracted >55% carnosic acid (RM-AK1) as well as dried rosemary

and essential oil.

Hainan Everlasting Biological Engineering Co Ltd is a large-sized biological

enterprise with their own scientific research, product development, production

and marketing facilities. The leading project is the research and development

of rosemary with 10 products developed from rosemary. They produce a range

of rosemary extracts CAROSE with carnosic acid concentrations ranging

from 20-50% by solvent extraction.

Ximen Kimy Biotechnology Co Ltd

The company supplies a series of products, including natural Cinnamaldehyde

products, Rosemary Oil, Rosemary Antioxidant, and Essential Oils of China.

The company has been in the field of essential oil and fine chemical industry

for ten years. The company has set up production and plantation bases, such

as Cassia Oil Factory with annual production of 50 tons in Rong County,

Guangxi Province; Natural essential oil in Yili region of Xinjiang

Municipality with rosemary, lavender, and peppermint. The company is also

building a chemical production base and rosemary plantation (200ha of

hillside) in Chanting County. The rosemary crops are grown on terraced

hillsides and at will be harvested fresh for distillation. The company is hoping

to extend this to the extraction of rosemary antioxidants from the crop after

80

distillation. At present the company has no experience with the production

and extraction of rosemary antioxidants.

The market for rosemary antioxidants, within China at present, is small as

most food and nutraceutical companies use synthetic antioxidants. Any

rosemary antioxidants are therefore most likely for export. However the

Chinese are becoming more health conscious and the internal market may

grow if the price is sufficiently low.

9.1.2. India

Rosemary is mostly cultivated as an irrigated and rainfed crop in higher

elevations. In Tamil Nadu, rosemary cultivation is mostly confined to the high

and middle elevations of Nilgiris district. Though there were some local

varieties of rosemary in the Nilgiris, scientists at the Horticultural Research

Station of the Tamil Nadu Agricultural University (TNAU), Vijayanagaram,

81

Uthagamandalam have produced a high-yielding disease-resistant variety

`Rosemary-Ooty (RM) 1

Companies such as pharmed medicare are already producing standardized

rosemary extracts for nutraceutical, pharmaceutical and cosmetic companies

by CO2 and solvent extraction. In addition companies such as the German

company Flavex have Indian subsidiaries Flavex Aromats India Ltd capable of

using SCF CO2 extraction to produce rosemary extracts.

9.1.3. South America

GRUPO CENTROFLORA - BRASIL was founded in 1957, in São Paulo, and

it is, presently, the South American leader in production and development of

vegetal standardised extract, for the pharmaceutical, cosmetic and food

industries. They produce a dry rosemary extract for the food industry,

rosemary essential oil for the cosmetic industry and a standardized dry

rosmarinic acid extract for the pharmaceutical industry. All extracts are

ethanol water extracted.

Natural Response is a company involved in the production and marketing of

natural extracts derived from unique Chilean plants or plants that grow

abundantly in Chile such as rosemary. The company is engaged in a

permanent collaboration with the Faculty of Engineering of the Catholic

University of Chile, and therefore has access to information on the latest

processes and leading edge technologies for the extraction and purification of

natural products.

9.1.4. Eastern Europe

Eastern Europe produces over 200,000Mtones of herb products/years with

Hungary and Romania the major producers. Rosemary is produced for the

dried herb and essential oil markets

9.1.5. Turkey

The production of dried rosemary leaf increases from 81 tonnes/year in 1990

to 540 tonnes in 1996

82

9.1.6. North Africa

Morocco exports 60 tonnes of its essential oil a year. To find ways of

exploiting this resource rationally and sustainably, Dr Ismaili-Alaoui

launched a company Tafilalet Arômes Méditerranée (TAROMED) in 1999

with Les Arômes du Maroc as a partner. Its first project, focused on

some10,000 hectares where the rosemary had never been exploited.

The Moroccan location is a strategic one because of the local availability of

raw materials such as rosemary and other mediterranean herbs and spices.

Naturex has a large production unit located in Casablanca dedicated to solvent

extraction. Six solvent extraction units process between 15 and 20 tons of raw

materials per day making this site is one of the largest in this field worldwide.

Tunisia

Heirs Brahim Belkhiria was founded in 1940. Their principal activity is the

production of essential oils and extracts from aromatic plants such as

rosemary.

Israel

Rosemary is generally grown in Israel in small fields of up to half a hectare

per farmer and is used only as a culinary herb. Research by Granot Regional

Enterprises has started on the large-scale cultivation of rosemary for

antioxidants. There are two companies exploiting rosemary production and

extraction in Israel RAD Natural Technologies Ltd and Lycored Natural

Products Industries, Ltd.

9.1.7. Australia/New Zealand

The Rural Industries Research and Development Corporation (RIRDC) has

identified key market areas for new phytopharmaceuticals which includes a

key product class of natural antioxidants With a large number of plants that

possessing antimicrobial and antioxidant activity R&D is concentrated on

those that can provide products that possess multiple actions such as rosemary,

which also has uses in the perfume industry

83

9.2. Contra indications of the use of rosemary antioxidants

9.2.1. Scientists (Toft et al) in the Human Nutrition department at The Royal

Veterinary and Agricultural University have shown that the use of phenolic-

rich extracts used as antioxidants in foods, such as green tea or rosemary

reduce the utilisation of dietary iron. The results were more significant for

green tea extract (30%) than for rosemary extract (<10%)

9.2.2. Allergic contact dermatitis from rosemary has been demonstrated in

Spain by Fernandez, L., S. Duque

84

a) SWOT ANALYSIS OF THE SUPPLY CHAIN FOR ANTIOXIDANTS FROM ROSEMARY

Area Strengths Weakness Opportunities Threats

Product Class / Market Sector

Natural / green image Wide market at present

in food, pharmaceuticals, nutraceuticals and cosmetics

Cost compared to synthetic antioxidanst

Market leaders not UK companies

Not enough UK marketing Availability of finance

Increasing health concern, changing lifestyle and consumer acceptance of natural antioxidants will foster demand for natural antioxidants in: Food, Pharmaceuticals, Nutraceuticals and Cosmetics

Speciality markets in plastics and paints: green additives in PVC and polyolefines

Plant-based products market increasing by over 8% NNFCC

Consortia between R&D, SME’s and industry;

Project management/Technology transfer

Regulationso increasingo uncertain

Internet sales: unregulated claims and supply

Price of other natural antioxidants eg tochopherol

Toxicology of antioxidants or degradation products

Currency fluctuations Non standardisation

of extracts

85

Horticulture and Agriculture

Strength Weakness Opportunities Threats

Traceability/ Good Agricultural Practice

General agricultural expertise

UK climate produces high levels of antioxidant

High value crop

Lack of connections between growers and end-users

Rosemary treated as a commodity so growers have no secure contracts for production.

Crop not bought on antioxidants content

Lag time to production High capital investment Production and

processing information is limited or not readily available

Crop care options for pests, diseases and weeds are limited

only 2.5% of value is in the raw material

Cost of production in UK high compared with Spain and N.Africa

Lack of R & D on production

Diversification of agriculture Contracts Known end-market High value / low volume Closed loop (plant to extract) Cooperatives Grower research Accredited production systems.

Commodity mentality Bandwagon

(oversupply) Irrigation Spanish and

N.African crops Low cost producers

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Strengths Weakness Opportunity Threats

Plant Selection, Breeding and Propagation

RAPFI research, High antioxidant concentration in selected accessions

Breeding Expertise/Biotechnology Not GM product

Poor returns for plant breeders

No Plant Variety Rights on Chemical content

Propagation materials expensive

Lack of breeding experience in this field

No Gene banks

Potential for GM Tissue culture Direct seed sown crop

Cheap imports of propagation stock

Extraction, Processing and Manufacturing

Traceability No solvent residues in

CO2 extracts

Expensive equipment Drying costs expensive in

the UK Few processing

companies in UK

Tailored extraction products Added value for growers for on farm processing Existing raw materials lower antioxidant content,

therefore higher costs of extraction Legislation: requiring high quality products Under-capacity on processing Processor research

Low cost producers, Eastern and Southern Europe, India, China

Control by major processors

Quality Assurance and Regulatory Authorities

UK production standards

Full traceability Quality Control Product consistency

Lack of Market standards Knowledge of the market by FSA Determination of Rosemary additive status

National branding/ Quality kite marking Production of quality products

Non-inclusion on EC list of additivres

11. Internet sales / substandard products

87

12. CONCLUSIONFrom this review of the market for antioxidants from rosemary there is obviously a

wide market for biological antioxidant products in food, neutraceuticals and

cosmetics. Tocopherol and ascorbic acid, either synthetic or natural are the most

widely used biological antioxidants but rosemary extract because of the cascade of

antioxidant products produced on oxidation is widely used.

Rosemary is not a widely grown crop at present. Most rosemary is wild harvested

from Spain and North Africa but many European countries have researched the crop’s

potential and have sufficient herb growing expertise to bring the crop into more

extensive production.

Rosemary extracts both alone and combined with tocopherol and ascorbic acid

compounds are extensively used in preserving foods particularly many snack products

and there is an increasing market in the production of pet foods. There is a wide

range of products in either liquid or powder form for use in lipid or aqueous

formulations and it is this ‘tailor made’ aspect of the rosemary extract that the market

seems able to exploit. The cosmetic market is also rapidly becoming a wide user of

rosemary extracts both for sun protection screens and anti ageing products. There is

also potential for the use of rosemary extract in the pharmaceutical market both as an

antioxidant to protect unsaturated vitamins and essential oils but also as a treatment in

its own right. However for the pharmaceutical market to have the confidence to

utilize rosemary extract as an antioxidant the extract will require purification and

standardization. Potentially there is a wide market for rosemary antioxidants in the

plastics and lubricants market but any uptake at present is limited by the variability of

rosemary extracts.

There are 18 European and 9 US companies extracting and formulating rosemary

extracts. Many of these companies are multinational with extensive markets and

production facilities in a number of countries. At present UK companies are not

widely represented in the production of rosemary extracts.

Two methods of extraction, either solvent extraction with ethanol or CO2 extraction

are used to produce rosemary extract. The major challenge for extractors will be to

extract high purity antioxidants at an economic cost.

There appear to be two major but related factors, which will affect the expansion of

the market for rosemary antioxidants in the future. The first is the status in the EU of

rosemary extract as an antioxidant additive. Until this is clarified the market for

88

rosemary antioxidants will remain limited, in food applications, to categories where

rosemary extract can be added as a spice or flavouring. Toxicological data on the

ADI (average daily intake) was submitted to the EFSA in November 2005 and the

outcome is awaited early in 2006. The second limiting factor, to the uptake of

rosemary extract, is the range of rosemary extracts offered to the market. This ranges

from rosemary oleoresin, containing essential oils, to CO2 extracted rosemary with

around 4% diterpenes to more refined solvent extracted products containing up-to

60% carnosic acid. Until there is some standardisation of the products then it is

impossible to see how the status of rosemary extract as an additive can be resolved.

Regulation and legislation, on additives, in Europe, the US and Worldwide is only

likely to become more restricted by the requirements of safety and efficacy. This is

less likely, however, to affect the market for rosemary antioxidants because of the

long tradition of use and the extensive research of the antioxidant cascade.

Threats to UK and European production will come from developing countries such as

China, and India with some of the multinationals already having facilities in these

countries. There is significant potential for the widespread production of rosemary in

North Africa through collaboration between North African, European and Israeli

companies. At present there is relatively little information on any contra indications

related to the intake or production of rosemary products.

This review has been funded by Defra to determine the supply-chain for rosemary

antioxidants in the UK. There are obviously a number of countries in North Africa,

China and India already producing significant amounts of dried rosemary and extracts

where production costs are much less than in the UK. However if the UK can

continue to produce rosemary with higher levels of rosemary antioxidants then a UK

product is viable. There is potential for these countries to introduce irrigation systems

but with the associated costs.

.

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European and United States Food Antioxidants Markets (2003) Frost and Sullivan

14. WEB SITES

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Directive 95/2/EC of the European Parliament and the Council of 20 February 1995

on Food Additives other than Colours and Sweeteners:

http://europa.eu.int/comm/food/fs/sfp/addit_flavor/flav11_en.pdf

General information on food additives (rules on labelling of additives, intake, etc):

http://europa.eu.int/comm/food/fs/sfp/addit_flavor/additives/index_en.html

http://www.eufic.org/en/quickfacts/food_additives.htm

Detailed information on legal issues is given on the following websites:

European Food Safety Authority: http://www.EFSA.eu.int

FAO/WHO Food Standards: http://www.codexalimentarius.net/

The E-Number listing for all additives can be found under:

http://www.eufic.org/en/quickfacts/food_additives.htm

FDA Food additives approval process

http://www.fda.gov/oia/embslides/additives/sld008.htm

Food Standards Agency http://www.food.gov.uk/

European patent Office http://www.espacenet.com/

US Patent Office http://www.uspto.gov/index.html

National Non Food Crops Centre http://www.nnfcc.co.uk/

RAPRA polymer research, technology and information centre http://www.rapra.net/

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