Food Chemistry 129 (2011) 171174

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Antioxidant effect of essential oils of rosemary, clove and cinnamon on hazelnut and poppy oils
Mehmet Musa zcan , Derya Arslan
Department of Food Engineering, Faculty of Agriculture, Selcuk University, 42031 Konya, Turkey

a r t i c l e

i n f o

a b s t r a c t
Antioxidant effects of essential oils from rosemary (Rosmarinus ofcinalis), clove (Syzygium aromaticum) and cinnamon (Cinnamomum zeylanicum) were determined on hazelnut and poppy oils. These essential oils were added to the oils at concentrations of 0.25% and 0.5%. Butylated hydroxyanisole (BHA) at 0.02% level served as standard besides the control groups for comparison. The samples were stored 50 C in darkness for 14 days. The antioxidant activity of the essential oils was determined by measuring peroxide values (meq O2/kg oil) at regular intervals. On the basis of peroxide value assay, the essential oils showed stronger antioxidant effect when compared to control groups. BHA was more effective than the essential oils, whilst it exhibited no antioxidative effect on the rst few days of storage. Amongst the investigated essential oils, the cinnamon oil was the most effective on retarding lipid oxidation of crude oils, which was followed by clove and rosemary oils. 2011 Published by Elsevier Ltd.

Article history: Received 26 September 2009 Received in revised form 4 October 2010 Accepted 1 January 2011 Available online 22 January 2011 Keywords: Antioxidant effect Spice Essential oil Hazelnut oil Poppy oil

1. Introduction Antioxidants commonly used in food products today are butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT). In recent years the safety of synthetic food additives, including the possible toxicity of these chemicals used as antioxidants has received increasing attention. So, there is need for other components to act as antioxidants and to render food products safer for mankind (Branen, 1975; Kahl & Kappus, 1993). As it is known, mainly the edible oils, fats and fatty foods can undergo deterioration in the course of the time depending on external factors such as heat, light, enzyme and trace metals. As a result of autoxidation especially which occurs with the effect of oxygen in the air, unpleasant taste and smell that are known as the signs of rancidity in oil occur. Autoxidation is an irreversible reaction which goes on spontaneously when it begins, and its rate is directly related to the oils unsaturation degree. The breakdown products formed after oxidation process such as peroxides, aldehydes and ketones shorten the shelf life of oils and turn products unacceptable for consumption (Akgl, 1989; Shahidi & Nazck, 1995). As a conclusion of these researches, in order to overcome the stability problems of oils and fats synthetic antioxidants, most of which have phenolic characteristic, such as BHA, BHT, ter-butyl hydroquinone (TBHQ) and gallates have been used as food additives for many years (Akgl, 1989; De Man, 1980). But recent reports reveal that these compounds may be implicated in many
Corresponding author. Tel.: +90 332 2232933; fax: +90 332 2410108.
E-mail address: mozcan@selcuk.edu.tr (M.M. zcan). 0308-8146/$ - see front matter 2011 Published by Elsevier Ltd. doi:10.1016/j.foodchem.2011.01.055

health risks (zcan & Akgl, 1995). For example, BHT causes liver expansion (Akgl, 1989). Also, it is well known that these compounds cause unpleasant taste and smells as they easily vaporise and degrade (Akgl, 1989; zcan & Akgl, 1995). To prevent these harmful effects of synthetic antioxidants, the use of antioxidants which are found in foods and various natural materials is recommended (zcan & Akgl, 1995). Researches on rosemary show that compounds which have antioxidant characteristic have phenol character and avonoids occupy an important part in them (Decker, 1997). On the other hand, it was reported that eugenol which is found in clove and cinnamon essential oils is an effective antioxidant compound in the researches (Farag, Badei, Hewedi, & ElBaroty, 1989a). It is doubtless, this effect is the result of eugenols phenolic structure (Weidenbrner, Hindrof, & Tsotsonos, 1990). The antioxidative effects of natural antioxidants on lipids were studied in recent years as a popular research area. Some of the effective factors on the antioxidative mechanism of natural compounds on lipids were expressed as the emulsion type of the system (Frankel, Huang, & Aeschbach, 1997; Hopia, Huang, Schwarz, German, & Frankel 1996), antagonistic and synergistic effects (Medina, Tombo, Satu-Gracia, German, & Frankel, 2002; zcan, 1999; zcan, 2000), temperature (Sature, Huang, & Frankel, 1995), concentration, hydrophilic or the lipophilic tendency of the system (Frankel, Huang, Aeschbach, & Prior, 1996; Schwarz et al., 2000) and the number and the place of connection of the hydroxyl groups in aromatic cycle (Chen, Chan, Ho, Fung, & Wang, 1996; Das & Pereira, 1990). Overall strongest activity of rosemary was not surprising because of various ndings reported on its stabilising effect (Chang,

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Ostric-Matijasvic, & Hsieh, 1977), and related active components such as carnosol, rosmanol, carnosic and ursolic acids etc. (Chen, Sui, & Ho 1992; Houlihan, Ho, & Chang, 1985; Inatoni, Nakatani, & Fuwa, 1983; Wu, Lee, Ho, & Chang, 1982). Kramer (1985) has identied eugenol as one of the major antioxidants present in clove. Farag, Badei, and El-Baroty (1989b) reported that clove and thyme essential oils exhibited antioxidant activity in rened cotton seed oil, with clove oil being superior to thyme oil. Little is known about the extent to which the spice essential oils may contribute to the antioxidant activity, although they have been extensively examined for their medicinal, culinary and antimicrobial properties (Akgl, 1993). Recently, pollution, stress and industrial food consumption increased the existence of free radicals. Antioxidants are the most effective compounds against free radicals. A lot of studies were carried out on antioxidants characteristics of several plants and corresponding derivatives such as essential oil and extracts. It is believed that detection of natural antioxidant sources and proper consumption of them in daily diet or use of isolated compounds in clinical practices would be benecial for healthy life (Farag, Badei, Hewedi, & El-Baroty, 1989a). The purpose of this work was to determine rosemary, cinnamon, clove essential oils antioxidant effects on hazelnut and poppy oil stored at 50 C in darkness.

2.4. Preparation of essential oil Essential oils of the samples were obtained by hydrodistillation method. The plant materials (about 100 g) were ground into small pieces and were placed in a ask (2 L) together with double distilled water (1.5 L). The mixture was boiled for 4 h. The extract was condensed in cooling vapour to collect the essential oil of each material. The extracted oil was dried over anhydrous sodium sulphate. All essential oils were kept at freezing temperature (18 C) until used for the analysis. 2.5. Antioxidant activity measurement The rate of oxidation was monitored by periodic determination of peroxide values of the oil stored at 50 C by using essential oils. A calculated quantity of the BHA and essential oils were added directly to the hazelnut and poppy oils at room temperature with the concentrations of 0.02%, 0.025% and 0.50% and dissolution was obtained by manual homogenisation for about 5 minutes. A control sample was prepared under the same conditions without addition of any antioxidant. Fifteen grams of each sample were stored in 10 100 mm open beakers at 50 C in the dark. For the determination of peroxide number, a given weight of hazelnut and poppy oils were dissolved in a mixture of acetic acid:chloroform (CH3COOH:CHCl3) (3:2,v/v), and saturated solution of KI (1 mL) was then added. The liberated iodine was titrated with sodium thiosulphate solution (0.01 N) in the presence of starch as an indicator (AOCS, 1990). 2.6. Statistical analyses

2. Material and methods 2.1. Plant material The samples [rosemary (Rosmarinus ofcinalis) leaves, clove (Syzygium aromaticum) buds and cinnamon (Cinnamomum zeylanicum) barks] were purchased from local market in Konya in Turkey. The samples were transported in polypropylene bags, and were dried to constant weight in room temperature for analyses.

Statistical analyses were performed using a one-way analysis of variance. A probability value of P < 0.05 was considered signicant _ (Psklc & Ikiz, 1989). 3. Results and discussion

2.2. Hazelnut and poppy oils Natural hazelnut and poppy oils without adding any antioxidant were kindly supplied by cool press processing. Peroxide values (meq O2/kg oil) of poppy and hazelnut oils were 1.5 and 1.8, respectively, at the beginning of experiment.

2.3. Butylated hydroxyanisole Synthetic antioxidant (Sigma) was preferred because of its common usage at vegetable oil producing companies to retard the oxidation.

Antioxidant effects of the spice essential oils on hazelnut and poppy oils were given in Tables 1 and 2. On the third day of the assay, all the oils showed antioxidant effect in varying degrees on hazelnut oil. Antioxidant activities of rosemary, clove and cinnamon oils were slightly weaker when compared to BHA added samples. A clear antioxidant effect of the essential oils was not observed on both hazelnut and poppy oils until the 10th day of storage when it is compared to control samples (Tables 1 and 2). After the 10th day, essential oil showed antioxidant effect at various degrees (Fig 1.). On the other hand, antioxidant effect increased together with essential oil concentration. After 10 days, 0.5% level of all essential oils on hazelnut oil maintained their antioxidant activity, exhibiting a marked effect in comparison with BHA (Table

Table 1 The effect of rosemary, cinnamon and clove essential oils on the peroxide value (meq O2/kg oil) of hazelnut oil stored at 50 C in darkness. Concentrations (%) Days 3 Rosemary Cinnamon Clove BHA Control
a

5 12.5 1.2 15 1.4 12.5 0.9 11.5 1.1 12 1.3 10.5 1.4 11.5 1.3 14 1.2

7 18.5 1.3 22 2.1 22.5 2.3 19.5 1.7 23 1.8 14.5 1.2 15.5 0.9 20.5 0.7

10 57.5 2.6 25 1.7 25 0.9 38.5 2.1 50 3.2 19 1.8 24 1.4 35 4.2

14 80 4.3 75 4.8 47 3.7 40 2.1 38.7 2.8 60 3.8 26 2.4 85 4.2

0.25 0.50 0.25 0.50 0.25 0.50 0.02

14.5 1.1a 11.5 0.9 11 0.6 11.5 1.5 11 1.2 10 0.4 6 0.2 9 0.8

Mean standard deviation.

M.M. zcan, D. Arslan / Food Chemistry 129 (2011) 171174 Table 2 The effect of rosemary, cinnamon and clove essential oils on the peroxide value (meq O2/kg oil) of poppy oil stored at 50 C in darkness. Concentrations (%) Days 3 Rosemary Cinnamon Clove BHA Control
a

173

5 31.5 4.1 36 3.7 30 4.5 35 3.6 34 3.1 34 2.6 19.3 2.1 33.5 3.2

7 88 6.6 87.5 5.4 62 3.2 85 4.3 78.5 3.7 71.5 4.2 34 3.1 76 4.2

10 207.5 12.5 332.5 13.7 231.5 21.6 234 21.4 287.5 27.2 305 26.4 138 15.3 413 28.6

14 537.5 25.3 565 24.6 472 22.1 575 17.8 523.5 32.4 552.5 33.2 240 23.8 812.5 28.4

0.25 0.50 0.25 0.50 0.25 0.50 0.02

18.5 1.4a 20 2.3 18.5 2.1 22 4.3 19 2.4 20.5 1.7 11.5 1.6 19 3.6

Mean standard deviation.

peroxide value (meq O2/kg oil)

90 80 70 60 50 40 30 20 10 0 1

(a)

8 days

10

11

12

13

14

15

Rosemary 0.25% Clove 0.25%

900 800 700 600 500 400 300 200 100 0 1 2 3 4

Rosemary 0.50% Clove 0.50%

Cinnamon 0.25% BHA 0.02%

Cinnamon 0.50% Control

peroxide value (meq O2/kg oil)

(b)

8 days

10

11

12

13

14

15

Fig. 1. The effect of rosemary, cinnamon and clove essential oils on the peroxide value (meq O2/kg oil) of hazelnut (a) and poppy (b) oils stored at 50 C in darkness.

1). As it is seen on Table 1, cinnamon essential oil showed the highest effect. When antioxidant effect of essential oils were compared for hazelnut and poppy oils, their effect was more remarkable for poppy oils (Table 2). Antioxidant effect of 0.5% level of clove oil was found higher compared to that of other essential oils (Table 2). The same level of this essential oil was effective on control group, too. The highest antioxidant activity was exhibited by 0.5% concentration of clove oil (Fig 1). All of spice essential oils were effective at 50 C in comparison with control. But when it was compared to BHA, the effect was at a very limited level. Farag, Badei, Hewedi, and El-Baroty (1989a) found the antioxidant effects of some spice essential oil in linoleic acid which emulsied in aqueous phase following the order like; clove > thyme > rosemary > cumin > sage > frenk cumin. zcan and Akgl (1995) re-

ported the antioxidant effects of the same spice volatile oils in sun ower oil in their study with an order like: summer savory > rosemary > sage > marjoram > oregano > anise > tarragon. Lagouri, Blekas, Tsimidou, Kokkini, and Boskou (1993) tested four Labiatae plant essential oils and carvacrol and thymol as the main components of the essential oils from this plant species in lard which was stored at 35 C; and they reported that the essential oils and their main components showed much higher antioxidant effect than BHA. Dorman, Peltoketo, Hiltunen, and Tikkanen (2003) determined the free radical scavenging activities of the aqueous extracts of O. vulgare L., R. ofcinalis and S. ofcinalis obtained from Finland. They reported the results as 0.335, 0.236 and 0.265 (IC50 [mg/ml]), respectively. In bulk corn oil, the rosemary extract, carnosic acid, rosmarinic acid, and a-tocopherol were signicantly more active than carnosol. In contrast, in corn oil-in-water emulsion, the rosemary

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M.M. zcan, D. Arslan / Food Chemistry 129 (2011) 171174 Frankel, E. N., Huang, S.-W., Aeschbach, R., & Prior, E. (1996). Antioxidant activity of rosemary extract and its constituents, carnosic acid, carnosol, and rosmarinic acid, in bulk oil and oil-in water emulsion. Journal of Agricultural and Food Chemistry, 44, 131135. Frankel, E. N., Huang, S.-W., & Aeschbach, R. (1997). Antioxidant activity of green teas in different lipid systems. Journal of American Oil Chemists Society, 74, 13091315. Houlihan, C. M., Ho, C. T., & Chang, S. S. (1985). The structure of rosmariquinone: a new antioxidant isolated from Rosmarinus ofcinalis L.. Journal of American Oil Chemists Society, 62, 9698. Hopia, A. I., Huang, S. W., Schwarz, K., German, J. B., & Frankel, E. N. (1996). Effect of different lipid systems on antioxidant activity of rosemary constituents carnosol and carnosoic acid with and without a-tocopherol. Journal of Agricultural and Food Chemistry, 44, 20302036. Inatoni, R., Nakatani, N., & Fuwa, H. (1983). Antioxidative effect of the constituents of rosemary (Rosmarinus ofcinalis L.) and their derivatives. Agriculture, Biology and Chemistry, 47, 521528. Kahl, R., & Kappus, H. (1993). Toxikologie der synthetischhen Antioxidantien BHA and BHT im Vergleich mit dem naturlichen Antioxidants Vitamin E. Zeits Lebensmittelunters Unters-Forschung, 196, 329338. Kramer, R. E. (1985). Antioxidants in clove. Journal of American Oil Chemists Society, 62, 111113. Lagouri, V., Blekas, G., Tsimidou, M., Kokkini, S., & Boskou, D. (1993). Composition and antioxidant activity of essential oils from oregano plants grown wild in Greece. Zeits Lebensmittelunters Unters-Forschung, 197, 2023. Medina, I., Tombo, I., Satu-Gracia, M. T., German, J. B., & Frankel, E. N. (2002). Effects of natural phenolic compounds on the antioxidant activity of lactoferrin in liposomes and oil-in-water emulsions. Journal of Agricultural and Food Chemistry, 50, 23922399. zcan, M., & Akgl, A. (1995). Antioxidant activity of extracts and essential oils from Turkish spices on sunower oil. Acta Alimentaria, 24(1), 8190. zcan, M. (1999). Antioxidant activity of rosemary (Rosmarinus ofcinalis L.) extracts on natural olive and sesame oils. Grasas y Aceites, 50, 355358. zcan, M. (2000). Antioxidant activity of sea fennel (Crithmum maritimum L.) essential oil and rose (Rosa canina) extract on natural olive oil. Acta Alimentaria, 29(4), 377384. _ _ Psklc, H., & Ikiz (1989). Introduction to statistics p. 333. Bornova, Izmir, Turkey: Bilgehan Press (in Turkish). Sature, M. T., Huang, S. W., & Frankel, E. N. (1995). Effect of natural antioxidants in virgin olive oil on oxidative stability of rened, bleached, and deodorized olive oil. Journal of American Oil Chemists Society, 72, 11311137. Schwarz, K., Huang, S. W., German, J. B., Tiersch, B., Hartmann, J., & Frankel, E. N. (2000). Activities of antioxidants are affected by colloidal properties of oil-inwater and water-in-oil emulsions and bulk oils. Journal of Agricultural and Food Chemistry, 48, 48744882. Shahidi, F. (1992). Antioxidants in food and food antioxidants. Nahrung/Food, 44(3), 158163. Shahidi, F., & Nazck, N. (1995). Food Phenolics. Pennsylvania: Technomic Publishing Company, Inc.. Weidenbrner, M., Hindrof, H., & Tsotsonos, P. (1990). Antifungal activity of avonoids against storage fungi the genus Aspergillus. Phytochemistry, 29(4), 21522156. Wu, J. W., Lee, M. H., Ho, C. T., & Chang, S. S. (1982). Elucidation of the chemical structures of natural antioxidants isolated from rosemary. Journal of American Oil Chemists Society, 59, 339345.

compounds were less active than in bulk oil, and the rosemary extract, carnosic acid, carnosol, and a-tocopherol were more active than rosmarinic acid (Frankel et al., 1996; Shahidi 1992). The results obtained in the present study showed that the antioxidant activity may be related to the presence of carvacrol, thymol and eugenol in essential oils. Cinnamon and clove essential oils had signicantly higher persistent antioxidant activity, probably due to the composition and conditions of the experiment (Farag, Badei, Hewedi, & El-Baroty 1989a). Further research is needed on the determination of the correlation between the antioxidant capacity and the chemical composition of the spice essential oils. Acknowledgement This work was supported by Seluk University, Ofce of Scientic Research Projects (S..-BAP, Konya-Turkey). References
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