Blackwell Science, LtdOxford, UKJFQJournal of Food Quality0146-9428Copyright 2005 by Food & Nutrition Press, Inc., Trumbu ll, Connecticut.

2005282109120Original Article ROSEMARY

SARDINE MINCEM. SERDAROLU and E. FELEKOLU

EXTRACTS AND ONION JUICE EFFECTS ON

EFFECTS OF USING ROSEMARY EXTRACT AND ONION JUICE ON OXIDATIVE STABILITY OF SARDINE (SARDINA PILCHARDUS) MINCE
( ( MELTEM SERDAROGLU1 and ELVAN FELEKOGLU Ege University Engineering Faculty Food Engineering Department zmir 35100, Bornova, I Turkey
Accepted for Publication December 20, 2003

ABSTRACT Sardine (Sardina pilchardus) mince was treated with rosemary extract (RE 300 ppm) and onion juice (OJ 1 mL/100 g) then stored at -20C for 5 months. Proximate composition, thiobarbutiric acid (TBA), free fatty acids (FFA) and peroxide value (PV) were determined on 0 and 15 days and 1, 2, 3, 4 and 5 months of storage. Fatty acid composition was also determined on 0 and 5 months of frozen storage. TBA, PV and FFA levels increased on all experimental groups due to the lipid oxidation. RE showed antioxidative effect on sardine mince during frozen storage as indicated by TBA, PV and FFA levels. Oxidation was delayed for 3 months by OJ treatment. At the end of 5 months storage, the TBA values in OJ treatment and control (C) treatment were out of consumable limits. After frozen storage of 5 months polyunsaturated fatty acid level decreased and saturated fatty acid level increased in the control treatment. No signicant change was observed in fatty acid composition in samples of RE and OJ treatments.

INTRODUCTION Sardine is an important species in Turkey; total catch was 20,500 tons in ( 1999 (Kasmo glu et al. 2003). It is generally consumed as fresh, canned or salted and also utilized as sh meal and oil. Lipid oxidation is one of the most

Corresponding author. TEL: +90 232 3882395; FAX: +90 232 3427592; EMAIL: mserdaroglu@food.ege.edu.tr

Journal of Food Quality 28 (2005) 109120. All Rights Reserved. Copyright 2005, Blackwell Publishing

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important factors responsible for quality deterioration of sh during both refrigerated and frozen storage. Lipid oxidation in muscle foods can be initiated by nonenzymic and enzymic reactions (Akhtar et al. 1998). Reactions between the by-products that are derived from lipid oxidation and proteins cause undesirable changes of food properties including protein denaturation, loss of protein solubility, alteration of texture and functional properties of protein and destruction of nutrient components (Verma et al. 1995; Akhtar et al. 1998). Frozen storage inhibits microbial spoilage and helps to slow down lipid oxidation. However, it does not inhibit lipid oxidation. Fish mince is less stable than whole sh due to the disruption of cellular membranes, which increases the rate of enzymatic and chemical reactions (Pastoriza et al. 1994). The rate and extent of oxidative deterioration depends on factors such as the storage period and temperature, saturation degree of fatty acids, presence of antioxidants or prooxidants and availability of oxygen (Ggs and Kolsarc 1992). The highly unsaturated fatty acids commonly found in seafood are particularly sensitive to oxidative changes during storage. Antioxidants are used by the food industry to delay the oxidation process (Brand-Williams et al. 1995). The most commonly used antioxidants are butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA). However, they are volatile and easily decompose at high processing temperatures and are synthetic chemicals. The possible toxicity of the synthetic chemicals used as antioxidants has been a subject of study for many years (Chang et al. 1977). Recently the food industry focused on the use of natural antioxidants, such as tocopherols, various spices and herbs, vegetable extracts and ascorbic acid. The antioxidant properties of spices and herbs are attributed to their phenolic contents (Akhtar et al. 1998). Many studies reported the effectiveness of these additives in retarding lipid oxidation (Inatani et al. 1983; ( Akhtar et al. 1998; Serdaroglu and Yldz-Turp 2001; Kamil et al. 2002). The use of rosemary as an antioxidant was reported by Rac and Ostric in 1955. More recently a patent was issued to Brener and Jobson in 1973 for the extraction of rosemary with oil (Chang et al. 1977). The antioxidative effect of rosemary is based on its phenolic diterpenes, carnosol and carnosinic acid as well as rosmanol, epirosmanol and iso rosmanol (Inatani et al. 1983; Schwarz and Ternes 1992). Many studies have demonstrated the effectiveness of rosemary extracts in retarding lipid oxidation (Cavoski et al. 1991; Liu et al. 1992; Boyd et al. 1993; Akhtar et al. 1998; Yldz-Turp and ( Serdaroglu 2002). Onions are often used as an additive in meat and sh patties. Younathan et al. (1983) reported that the presence of avonoids, ascorbic acid and sulfur compounds in onion extract probably contributes to the antioxidant effect of onion extract. The objective of this study was to determine the effect of frozen storage on oxidative quality of sardine mince

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(Sardina pilchardus) and to measure the antioxidant effectiveness of rosemary extract and onion juice.

MATERIALS AND METHODS Material The samples of sardine (Sardina pilchardus) each approximately in weight 6080 g and 1416 cm in length were obtained from a local sh market in Izmir (in the Aegean Region of Turkey). Fish were iced and transported to the Food Engineering Department, Ege University, in Izmir and were lleted on the same day. The llets were minced using a meat grinder with a 3 mm hole plate. The following treatment groups were prepared: 300 ppm rosemary extract (Dragoco 9/037174), 1 mL/100 g onion juice (prepared by pressing white large onions with food processor in laboratory conditions), control batch ([C] without antioxidant). Batches were ground twice by using the meat grinder to ensure an even distribution of rosemary extract (RE) or onion juice (OJ) with the sh mince. All samples weighed 250 g each and were packed in polyamide/polyethylene bags and than stored at -20C 2C for 5 months. Samples were randomly drawn for analysis at the evaluation periods. Thiobarbuturic acid value (TBA), peroxide value (PV) and free fatty acids (FFA) were tested after 0 and 15 days and 1, 2, 3, 4, 5 months of storage. Fatty acid prole of samples was evaluated on 0 and 5 months of storage. Zero time (day 0) samples were taken after 24 h of mincing, monthly evaluated samples were taken on the last day of each month. All analysis were done on three packages.

METHODS Proximate Composition Moisture content was measured using the oven-drying procedure according to the AOAC (1990). Fat content was determined by the chloroformmethanol extraction according to Flynn and Bramblett (1975). Protein content was determined (Anon 1979). Ash content was measured according to the AOAC (1990) procedure. Lipid Oxidation Parameters Thiobarbuturic acid values were determined according to Tarladgis et al. (1960); the results were expressed as mg malonaldehyde equivalents/kg of

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sample. Free fatty acids and peroxide value were assessed by the AOAC (1990) method. Fatty Acid Composition Fatty acid composition was determined according to the method outlined by Morrison and Smith (1964). Sardine lipids were converted to their fatty acid methyl esters by heating the lipids in a mixture of benzene and boron triuoride methanol complex solution at 85C for 30 min. Methyl esters were analyzed by gas liquid chromatography. As outlined by Wada and Fang (1992) a decline in the ration of eicosapentaenoic acid (EPA) + docosahexaenoic acid (DHA)/16 : 0 fatty acid was measured to elucidate oxidative deterioration of polyunsaturated fatty acid in sh lipids. Statistical Analysis The trial was performed twice and all analysis was done on three packages at each trial. Data were analyzed by ANOVA using general linear model (GLM) procedure of SPSS (1997) V.8 with a signicance level of (P < 0.05). Differences among means were determined by Least Signicance Differences (P < 0.05).

RESULTS AND DISCUSSION The average proximate composition of the sardine mince for protein, fat, moisture and ash was 16.2, 5.2, 77.2 and 1.2%, respectively. Those values were generally in line with the results reported by Kilin (2003) and Gokoglu et al. (1998). Changes in TBA values of treatment groups stored at -20C are given in Fig. 1. Initial TBA values of RE, OJ and C treatments were found to be 0.95, 1.02 and 1.26 mgma/kg, respectively. All samples showed an increased TBA value with storage (P < 0.05) period. No differences were found in TBA values of treatment groups at the rst (initial) and second evaluation period (P > 0.05). The TBA values of RE treatment and OJ treatment were signicantly lower than that of the control after 1 month of storage. The mean TBA value was 4.17 mgma/kg for the control samples at 1 month. After 3 months of storage no differences were found in TBA values between the control and OJ treatments. TBA values of the control samples increased sharply in frozen storage from day 15 to 30. Samples treated with RE showed a sharp increase in TBA values between month 2 and 3. However, at the end of the storage the lowest TBA value was recorded as 5.97 mgma/kg for the RE treatment. TBA values indicated that control samples and samples with added OJ were more

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RE OJ C

10 TBA (mgma/kg) 8 6 4 2 0 0 1 2 3 4 5 Storage (month)

FIG. 1. CHANGES IN TBA VALUES OF SARDINE MINCES STORED AT -20C

rancid than samples treated with RE throughout the storage time at -20C. OJ treated samples had TBA values in acceptable limits after 4 months of storage; however, there were no differences in TBA values between the OJ-treated samples and control samples at the end of the storage period. Similar to our ndings Younathan et al. (1983) reported the antioxidative effect of onion juice for frozen shark and mackerel muscle. Antioxidative activity of onion juice may be attributed to the high level of ascorbic acid, sulfur and avonoid compounds. At the end of the storage period the TBA values in OJ and C group were quite high, which Sinnuber and Yu (1977) reported as acceptable for frozen seafood. Changes in peroxide values of sardine minces likewise occurred. At zero and 15 days of storage there were no signicant differences in peroxide values of the treatment groups. Peroxide values of RE, OJ and C treatments were 10.94, 11.96 and 14.24 meqPO/kg, respectively. High PV levels of lipids from sardine during the initial storage stages may be attributed to the high degree of unsaturation of fatty acids and the mincing process. It has been reported that mincing sh muscle creates a larger surface area and then the lipids are easily oxidized (Pastoriza et al. 1994). The mincing process disturbs the muscle membrane system, thereby exposing the lipid components to oxygen, or causes other reactions (Love and Pearson 1976). The PV for all samples increased during frozen storage (P < 0.05). Treating with RE or OJ showed the same effect on peroxide value at each storage step. The control samples had the highest peroxide values at each storage time (P < 0.05). The mean level of PV for the RE treatment was 19.15 meqPO/kg after 5 months of storage. The PV value was lower in the OJ added samples than the control samples at each evaluation period. PV levels of samples stored at -40C

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increased more rapidly than the sample stored at 0C (Hwang and Regenstein 1996). Similar to our results Wada and Fang (1992) reported that PV levels of rosemary extract added to sardine oil were lower than -tocoferol added samples. In our research after 5 months of storage, the lowest PV was observed for sardine mince treated with RE. Ackman and Gunnlakgsdattir (1992) reported that PV of mackerel llets ranged from 20 to 30 meqPO/kg after 5 months of storage at -15C. In our study peroxide value for all treatment groups did not exceed 30 meqPO/kg. FFA formation as a result of lipid hydrolysis (triglyseride and phospholipid classes) has provided a suitable means for assessment of sh damage during frozen storage (de Koning and Mol 1991; Hwang and Regenstein 1996). FFA values of samples stored at -20C are given in Fig. 2. FFA values increased signicantly as a function of time (P < 0.05). At zero time the mean FFA level was recorded 5.15 for RE treated sample, 5.92 for OJ treated sample and 7.57 mmole/g for the control sample. Treatment with RE or OJ signicantly affected FFA levels of samples during storage. At zero time and on day 15 there were no signicant differences among treatment groups (Fig. 3); however, FFA level had a sharp increase in control samples after 1 month of storage. No differences were found in FFA levels between OJ treated and control samples after 3 months of storage (P > 0.05). At the end of storage period the lowest FFA level was found in samples treated with RE. FFA develops in sh even at -29C although at a very slow rate (Olley et al. 1969). The increase is due to the hydrolysis of phospholipids and triglyserides by the action of lipases and phospholypases (Oshima et al.

RE OJ 30 25 C

PV (meqPO/kg)

20 15 10 5 0 0 1 2 3 4 5

Storage (month)

FIG. 2. CHANGES IN PV (meqPO/kg) VALUES OF SARDINE MINCES STORED AT -20C

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RE 25 OJ C

FFA (mmole/g)

20 15 10 5 0 0 1 2 3 4 5

Storage (month)
FIG. 3. CHANGES IN FFA VALUES OF SARDINE MINCES STORED AT -20C

1984; Fazal and Srikar 1989). Abdel-aal (2001) reported that Nile karmout sh (Claries lazera) mince treated with antioxidants and stored at -18C showed signicant increment in FFA levels and no effect of added antioxidants on FFA levels was observed. Hwang and Regenstein (1996) did not detect any signicant changes in FFA levels of mackerel mince patties stored under vacuum at -40C. Accumulation of FFA in frozen sh is related to some extent with lack of acceptability, because FFA are known to cause deterioration by interacting with proteins, strongly interrelated with lipid oxidation (Han and Liston 1989; Auburg 1999) and affect taste or odor. Fatty acid proles of sardine mince treatments are given in Table 1. There was similarity in fatty acid proles among the treatment groups. The major fatty acids in the total lipids of sardines were palmitic acid (16 : 0), stearic acid (18 : 0), palmitoleic acid (16 : 1), eicosatrienoic acid (20 : 3 n-3), eicosapentaenoic acid (20 : 5 n-3) and docosahexaenoic acid (22 : 6 n-3). Signicant differences were observed in fatty acid proles of control treatment before and after storage whereas no signicant differences were recorded for the other treatment groups (RE or OJ) in any class of fatty acid at month 5. In control samples saturated fatty acid (SFA) percent increased from 32.17 to 42.1 whereas polyunsaturated fatty acid (PUFA) percent decreased from 43.81 to 32.78. The decrement in PUFA percent reects enzymatic hydrolysis of sardine lipids. Similar to our results, Kundak (1979) reported that SFA percent increased from 31.75 to 37.48 in mullet llets after 18 months storage at -18C. SantAna and Manchini-Filho (2000) showed that the use of antioxidants altered fatty acid composition of sh llets. Fish muscle contains characteristic high amounts of EPA and DHA. Since EPA and DHA are very easily oxidized because of their high unsaturation, a decline in the ratio of EPA + DHA/16 : 0 fatty acid has been used to elucidate oxidative deterioration of polyunsaturated fatty acid in sh lipids (Wada and Fang 1992). In

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TABLE 1. FATTY ACID PROFILE OF SARDINE MINCES STORED AT -20C OJ 5th month 3.99 0.21 19.76 0.13 7.68 0.09 13.22 0.12 1.95 0.21 3.0 1.21 3.22 0.43 0.35 0.21 8.02 0.32 10.31 0.21 0.35 0.21 16.34 0.12 31.43 0.13 15.17 0.23 41.59 0.12 56.76 0.11 11.81 0.09 1.34 0.12 4.34 0.21 21.17 1.54 8.09 1.11 12.06 0.14 2.22 0.21 3.59 0.17 2.24 0.34 0.28 1.22 10.53 1.13 11.38 1.01 0.49 1.12 16.3 0.99 33.6 1.32 14.28 2.01 44.88 1.11 59.16 0.23 7.24 0.45 1.31 0.53 5.99 1.21 20.65 1.08 8.02 0.92 11.79 0.13 2.33 0.87 3.42 0.78 2.18 0.45 0.23 1.98 8.45 0.78 11.30 0.56 0.42 0.99 16.65 0.56 34.66 1.22 14.12 1.76 42.65 0.03 56.77 0.98 8.57 0.92 1.35 0.45 4.56 0.78 19.11 1.76 8.50 1.22 12.54 1.54 2.33 1.22 3.60 1.09 2.27 0.45 0.31 0.69 10.42 1.09 10.45 1.09 0.55 1.02 16.21 1.76 32.17 0.45 14.87 0.99 43.81 0.04 58.68 1.02 9.15 0.78 1.39 0.22 0 day 5th month 0 day C 5th month LU and E. FELEKOG LU M. SERDAROG 3.67 1.96 24.67 0.58 13.76 0.01 10.34 0.32 1.45 0.46 2.56 0.37 1.87 0.34 0.26 0.11 8.98 0.23 6.36 0.42 0.33 1.03 12.42 1.04 42.1 1.09 11.79 2.13 32.78 0.21 44.57 0.23 13.33 0.92 0.76 0.14

Fatty acid (g/100 g total fatty acids)*

RE

0 day

14 : 0 16 : 0 18 : 0 16 : 1 18 : 1 18 : 2 18 : 3 n-3 20 : 2 20 : 3 n-3 20 : 5 n-3 (EPA) 22 : 5 n-3 22 : 6 n-3 (DHA) SFA MUFA PUFA TUFA Others EPA + DHA/16 : 0

4.99 0.13 19.11 0.11 6.51 0.23 13.86 0.32 2.61 0.43 3.48 0.12 3.73 0.18 0.49 0.21 10.20 0.14 10.44 0.09 0.51 0.08 17.13 0.12 30.11 0.13 16.47 0.13 45.98 0.11 62.45 0.12 7.44 0.05 1.44 0.12

* Mean SD. RE, rosemary extract; OJ, onion juice; C, control; EPA, eicosapentaenoic acid; DHA, docosahexsaenoic acid; SFA, saturated fatty acid; MUFA, monounsaturated fatty acid; PUFA, polyunsaturated fatty acid; TUFA, total unsaturated fatty acid.

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control samples mean EPA + DHA/16 : 0 value decreased from 1.39% to 0.76% at the end of storage; no changes were observed in EPA + DHA/16 : 0 value for RE or OJ treatments after 5 months of storage. Beltran and Moral (1990) observed an increment in EDA and DHA levels for sh llets stored at -18C for 180 days. Younathan et al. (1983) showed the effect of adding onion extract on the stability of PUFA of shark mince. Dissimilar to our results according to Boyd et al. (1993), fatty acid composition of RE treated cooked sh llets was not different than control llets after storage at -20C. Thus, differences may be attributed to cooking of sardine mince in their research.

CONCLUSIONS Results of our investigation revealed that 300 ppm rosemary extract retarded oxidative changes in frozen sardine mince. Onion juice (1 mL/100 g) was not as effective as rosemary extract on oxidative stability. Adding onion juice retarded rancidity development for 3 months of storage. Further research is necessary to study the effects of different levels of onion extract on oxidative stability of frozen sh mince.

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