Lebensm.-Wiss. u.-Technol.

, 34, 380 } 383 (2001)

Thermal Kinetics of Colour Degradation and Storage Characteristics of Onion Paste

J. Ahmed and U. S. Shivhare*

Department of Food Science & Technology, Guru Nanak Dev University, Amritsar-143005 (India) (Received February 29, 2000, accepted February 13, 2001)

The kinetics of colour degradation at selected temperatures and ewects of packaging materials and storage temperatures on colour of onion paste were determined. Colour change during thermal processing of onion paste followed xrst-order reaction kinetics. The tristimulus colour value combination La/b adequately described the colour degradation. Dependence of the rate constant during thermal processing of onion paste obeyed the Arrhenius relationship. The activation energy for onion paste was estimated to be 16.2 kJ/mol. The total colour of onion paste was signixcantly awected (P40.05) by packaging materials, temperature and duration of storage. The paste was more stable at low temperature (5 3C) than at higher temperatures (25 3C) with respect to colour, and colour degradation was minimum when the paste was packed in a high-density polyethylene pouch.

2001 Academic Press Keywords: onion paste; kinetics; colour; packaging materials; storage

Introduction Onion (Allium cepa L.) is valued for its therapeutic properties and possesses a strong characteristic aroma and #avour which makes it an important ingredient during food processing (Augusti et al., 1996; Dron et al., 1997). The characteristic #avour of onions comes primarily from volatile organic sulphur compounds released enzymatically by the action of allinase on several naturally occurring amino-precursors during comminution. The primary reaction products are thiosul"nates, which are heat labile and dissociate on heating to form di- and tri-sul"des and other sulphur compounds that have been associated with cooked onion #avour (Block & O'Conner, 1974). Onion paste is one such product that is convenient to use and could retain the original colour and #avour in a semi-solid form. Colour is an important attribute because it is usually the "rst property the consumer observes (Saenz et al., 1993). Various factors are responsible for the loss of colour during processing of food products. These include non-enzymatic and enzymatic browning and process conditions such as pH, acidity, packaging material and duration and temperature of storage. To optimize the process, it is important to determine the kinetic parameters (reaction order, reaction rate constant, activation
* To whom correspondence should be addressed. E-mail: jasahmed@ redi!mail.com

energy) for colour change (Weemaes et al., 1999). The colour kinetics of food products is a complex phenomenon and dependable models to predict experimental colour change, which can be used in engineering calculations, are limited. Therefore experimental studies and application of various simpli"ed models to represent the behaviour are required. Anthocyanin is the major pigment responsible for colour in red onions and the major compounds identi"ed were cynidin-3-glucoside, cyanidin-3-diglucoside and peonidin glucoside (Kalra, 1987). Onions contain reducing sugars and amino acids that enhance non-enzymatic browning during thermal processing (Berk, 1980; Shin & Bhowmick, 1994). Several authors have studied the colour kinetics of food materials during thermal processing in terms of changes in Hunter tristimulus colour values , a and b (Shin & Bhowmik, 1994; Berry, 1998; Kajuna et al., 1998; Nanke et al., 1999; Weemaes et al., 1999; Ahmed et al., 2000). Hence, if the kinetics of colour degradation is determined and the order of colour change is established, the total colour can be used to evaluate quality of food material during thermal processing. No information is available on thermal kinetics of colour degradation and storage behaviour of onion paste. The present study was undertaken to investigate the kinetics of colour degradation of onion paste at selected processing temperatures using the Hunter colour scale values (, a, b) and the e!ects of temperature and packaging material on colour during storage of onion paste.

0023-6438/01/060380 # 04 $35.00/0 2001 Academic Press

doi:10.1006/fstl.2001.0771 All articles available online at http://www.idealibrary.com on

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Materials and Methods Preparation of paste Onion bulbs (variety: Pusa Red) were obtained locally, peeled, cut and immediately processed into puree using a laboratory size grinder. The puree was passed through a 14-mesh sieve to obtain the product of uniform consistency. The puree was held at room temperature (25$1 3C) for 1 h in a covered container to facilitate enzymatic action for colour and #avour development (Dron et al., 1997). Common salt (sodium chloride) was added (5, 7 and 10 g/100 g) to onion puree to increase its total soluble solids (TSS). Sensory analysis results indicated consumer's preference for the puree containing 10% salt. The paste was therefore prepared by adding 10% salt. Onion puree had a pH of 5.45 and "nal pH of the paste was adjusted to 3.9 by adding desired quantity of citric acid solution. It has been established that citric acid acts as an anti-oxidant and an acidi"ed food (pH (4.6) requires mild heat treatment to make it shelf stable (Garcia et al., 1999). Thermal kinetics Thermal kinetics of onion paste was studied by heating it at selected temperatures (60, 70, 80 and 90 3C) for a residence time of 0 }20 min. Approximately 200 g paste was weighed and transferred into a 250 mL glass beaker and covered with a lid. The beakers containing paste were placed in a constant temperature water-bath at selected temperatures ($1 3C) and periodically agitated to ensure uniform temperature throughout the bulk of sample. The temperature of the sample at its geometric centre was monitored using a thermometer. The beakers were heated for 0, 5, 10, 15 and 20 min respectively after the paste at its geometric centre attained the desired temperature. The samples were transferred to an ice water bath immediately after the thermal treatment. Colour measurement Colour measurement was carried out using a Hunter colourimeter model D25 optical sensor (Hunter Associates Laboratory Inc., Reston, VA, U.S.A.) on the basis of three colour values, namely , a and b. The instrument (453/03 geometry, 103 observer) was calibrated against a standard white reference tile ("90.55, a"!0.71, b"0.39). A glass cell containing the heat-treated paste was placed above the light source and covered with a white plate and , a, b values were recorded.

with C measured Hunter colour value (, a, b) or a combination of these, dimensionless; C measured colour  value(s) at zero time, dimensionless; k rate constant during heating (min\), t heating time (min). The Arrhenius equation to relate the dependence of the rate constant with temperature is represented by Eqn [2]: exp (!E/RT) Eqn [2]  with k frequency factor (min\), E"activation energy  (kJ/mol), R"universal gas constant (8.314 J/mol/K), T"absolute temperature (K). k "k

Storage studies The paste was thermally processed at 80 3C for 15 min and packaged immediately in selected containers [glass, polyethylene terephthalate (PET) and high-density polyethylene (HDPE) pouch]. Storage studies were carried out at room temperature (25$1 3C) and refrigeration temperature (5$1 3C) respectively for 71 days. The samples were analysed periodically for colour, TSS, pH and titratable acidity. Physico-chemical properties Total soluble solids (3Brix) and pH were determined using a Refractrometer (Atago, Japan) at 20 3C and a pH meter with glass electrode (Systronics, India) respectively. Titratable acidity was measured in terms of citric acid by titrating the diluted paste against 0.1 N NaOH solution using phenolapthalein indicator (Rangana, 1986). Sodium chloride was determined by titration with silver nitrate (Rangana, 1986). Water activity (a ) of the prod uct was determined following the method of Landrock and Proctor (1951). Each experiment was replicated twice and the average values were used in the analysis. Statistical analysis The in#uence of time and temperature of storage on colour was determined by paired samples t-test using SPSS (1996) software. Signi"cance of di!erences was de"ned at P40.05. Results and Discussion The pH and acidity of onion paste were 3.9 and 0.41% respectively. TSS and water activity values were 16.53 Brix and 0.84 respectively. The paste contained 9.3% sodium chloride. TSS, titratable acidity and pH of onion paste did not change signi"cantly (P'0.05) during storage. The initial Hunter colour , a and b values of onion paste were 39.48, 7.3 and 4.20 respectively. Degradation in colour of onion paste was observed during thermal processing. Red pigment decreased and product turned brown with time as re#ected by decrease in both a and values. There was a corresponding increase in the b value. Therefore, di!erent combinations of tristimulus , a, b colour values were tested to describe the total colour change of onion paste. These combinations were subjected to linear regression with respect to

Model for computation of change in colour Degradation of colour pigments has been shown to follow the "rst-order reaction kinetics (Huang & Von Elbe, 1985; Hutchings, 1994; Shin & Bhowmik, 1994; Toledo, 1997; Ahmed et al., 2000). Therefore, it was reasoned that the colour change due to thermal treatment of onion paste follows the "rst-order reaction kinetics, represented by Eqn [1] ln (C/C )" !k ) t  Eqn [1]

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Table 1 Regression coe$cients of Eqn [1] for selected combinations of the Hunter colour scale values for onion paste at 60 3C
Combination ab a/b /ab b/a Correlation coe$cient 0.832 0.980 0.967 0.911 Standard error 0.0024 0.0015 0.0017 0.0021

Fig. 3 E!ect of packaging materials on total colour of onion paste packed in () glass container, () PET container, () HDPE pouch, (!) Eqn [3] at 5 3C

Fig. 1 Temporal variation of Hunter colour value ratio (a/b)/( a b ) of onion paste at selected temperatures ()    60 3C, () 70 3C, () 80 3C, () 90 3C, (!) Eqn [1]

processing of green chilli puree Ahmed et al. (2000) found ;a;b to be the best combination for describing the total colour degradation. E!ect of temperature on the rate constant is shown in Fig. 2. The dependence of the rate constant on temperature obeyed the Arrhenius relationship (Eqn [2]). Correlation coe$cient for the linear regression analysis equaled 0.99. The computed value of activation energy was 16.2 kJ/mol which is in range with the value reported by Ahmed et al. (2000) (16.0 kJ/mol for lye-treated green chilli puree).

Fig. 2 The Arrhenius plot relating rate constant to process temperature (!) Eqn [2]

Storage characteristics Colour of onion paste was signi"cantly a!ected (P40.05) by both packaging materials and conditions during storage. Change in colour of paste was minimum in HDPE pouch but maximum while it was stored in glass containers at both 5 and 25 3C. A typical behaviour is shown in Fig. 3. Air was excluded before sealing the HDPE pouches, while glass and PET bottles had head space. Presence of head space air may therefore have caused oxidation leading to colour change during storage. The product was stable at refrigerated temperature (5 3C) as compared to 25 3C (Fig. 4). This may be due to faster rate of colour degradation at higher temperature (Sagar & Maini, 1997). Variation in colour of paste during storage was represented by Eqn [3] ln (a/b)/( a /b )" !k ) t Eqn [3]      with k rate constant during storage (day\), t storage   time (days) (Table 2). The solid lines in Figs 3 and 4 represent Eqn [3]. It is obvious from these "gures that Eqn [3] described adequately the variation of total colour of onion paste with duration of storage. This study has veri"ed the previous "ndings (Bajaj et al., 1997; Berk, 1980) that red pigment (anthocyanin) degrades (manifested by decrease in the Hunter a value) and non-enzymatic browning takes place (decrease in the and increase in the b values) during thermal processing and the extent of variation was governed by processing temperature. Further, the total colour (a/b), expressed by incorporating all three Hunter colour (, a, b) values,

time as represented by Eqn [1] and the coe$cients were determined (Table 1). Correlation coe$cient and standard error values were used as the basis to select the combination which best described the "rst-order reaction for the entire temperature range. It was found that a/b was the most appropriate combination, which described closely the "rst-order reaction kinetics of colour degradation of onion paste (Fig. 1). The coe$cient of correlation values were between 0.980 and 0.997 while the standard error values were less than 0.0016. Shin and Bhowmik (1994) have reported similar observations while working on thermal processing of pea puree. They reasoned that all the three parameters should be combined together and found a/b as the optimum combination to describe the total colour degradation. While working on thermal

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Table 2 Values of the coe$cients of Eqn [3]

Packaging material Glass container a b ? PET container. @ HDPE pouch. BERK, Z. Introduction to Biochemistry of Food. Elsvier Scienti"c Publishing Co. Amsterdam, The Nederlands (1980) BERRY, B. W. Cooked color in high pH beef patties as related to fat content and cooking from the frozen or thawed state. Journal of Food Science, 63, 797 } 800 (1998) BLOCK, E. AND O'CONNER, J. The chemistry of alkyl thiosul"nate esters VI preparation and spectral studies. Journal of American Chemical Society, 96, 3921 } 3929 (1974) DRON, A., GUYER, D. E., GAGE, D. A. AND LIRA, C. T. Yield and quality of onion #avour oil obtained by supercritical #uid extraction and other methods. Journal of Food Process Engineering, 20, 107 } 124 (1997) GARCIA, P., BRENES, M., ROMERO, C. AND GARRIDO, A. Color and texture of acidi"ed ripe olives in pouches. Journal of Food Science, 64, 248 } 251 (1999) HUANG, A. S. AND VON ELBE, J. H. Kinetics of the degradation and regeneration of betanine. Journal of Food Science 50, 1115 } 1120, 1129 (1985) HUTCHINGS, J. B. Food Colour and Appearance. U.K.: Blackie Academic and Professional Publications (1994) KAJUNA, S. T. A. R., BILANSKI, W. K. AND MITTAL, G. S. Color changes in bananas and plantains during storage. Journal of Food Processing & Preservation, 22, 27 } 40 (1998) KALRA, C. L. Harvesting, handling, storage, chemistry and technology of onion (Allium cepa Linn) } a resume. Indian Food Packer, 41, 17 } 53 (1987) LANDROCK, R. H. AND PROCTOR, B. E. A new graphical interpolation method for obtaining humidity equilibrium data with special reference to its role in food packaging studies. Food echnology, 5, 332 (1951) NANKE, K. E., SEBRANEK, J. G. AND OLSON, D. G. Color characteristics of irradiated aerobically packaged pork, beef and turkey. Journal of Food Science, 64, 272 } 278 (1999) RANGANA, S. Handbook of Analysis and Quality Control for Fruit and <egetable Products. New Delhi: Tata McGraw-Hill Publishers (1986) ROCHA, T., LEBART, A. AND MARTY-AUDOUIN, C. E!ect of pretreatments and drying conditions on drying rate and color retention of basil. ebensmittel-=issenschaft und-echnologie, 26, 456 } 463 (1993) SAENZ, C., SEPULVEDA, ARAYA, E. AND CALVO, C. Color changes in concentrated juices of prickly pear (Opuntia ,cus indica) during storage at di!erent temperatures. ebensmittel-=issenschaft und-echnologie, 26, 417 } 421 (1993) SAGAR, V. R. AND MAINI, S. B. Studies on the packaging and storage of dehydrated onion slices. Indian Food Packer, 51, 5 } 10 (1997) SHIN, S. AND BHOWMIK, S. R. Thermal kinetics of colour changes in pea puree. Journal of Food Engineering, 27, 77 } 86 (1994) TOLEDO, R. T. Fundamentals of Food Process Engineering. India: CBS Publication (1997) WEEMAES, C. A., OOMS, V., LOEY, A. M. AND HENDRIKX, M. E. Kinetics of chlorophyll degradation and color loss in heated broccoli juice. Journal of Agricultural and Food Chemistry, 47, 2404 } 2409 (1999) Storage temperature 25 3C 5 3C 25 3C 5 3C 25 3C 5 3C k  !0.0673 !0.0175 !0.0328 !0.0069 !0.0341 !0.0060 Correlation coe$cient 0.989 0.991 0.982 0.994 0.955 0.963 Standard error 0.0022 0.0005 0.0014 0.0002 0.0022 0.0004

Fig. 4 E!ect of storage temperature on total colour of onion paste packed in HDPE pouch at () 25 3C, () 5 3C, (!) Eqn [3]

represented well the degradation process in both thermal processing and storage. Therefore the tristimulus colour measurement may be incorporated for on-line quality control as advocated by Rocha et al. (1993). Results of this study indicated that onion paste should be stored in HDPE pouch at 5 3C (Fig. 4).

Conclusions The kinetics of colour change of onion paste followed "rst-order reaction. The combination a/b can be used to predict the degradation of total colour of onion paste. The rate constant increased with temperature and the dependence could be described using the Arrhenius equation. Colour of paste was better when it was stored in HDPE pouch at 5 3C. This study clearly demonstrates the advantage of objective measurement to study colour changes of onion paste during both thermal processing and storage.

References
AHMED, J., SHIVHARE, U. S. AND RAGHAVAN, G. S. V. Rheological characteristics and kinetics of color degradation of green chilli puree. Journal of Food Engineering, 44, 239 } 244 (2000) AUGUSTI, K. T. Therapeutic values of onion and garlic. Indian Journal of Experimental Biology, 64, 334 } 336 (1996) BAJAJ, K. L., KAUR, G., SINGH, G. AND GILL, S. P. S. Lachrymatory factor and other chemical constituents of some varieties of onion (Allium cepa L.). Journal of Plant Foods, 3, 199 } 203 (1979)

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