1randd.defra.gov.uk/document.aspx?document=nf0609… · web viewthe rosemary extract is produced...
TRANSCRIPT
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
17
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 [email protected]
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 [email protected]
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: [email protected]
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 [email protected]
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: [email protected]
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: [email protected]
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: [email protected]
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: [email protected]
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 [email protected]
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 [email protected]
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: [email protected]
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 [email protected]
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 [email protected]
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
UK contact
Tel +44 (0) 1638 715011, Fax +44 (0) 1638 715031
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: [email protected]
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: [email protected]
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)
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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
86
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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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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