Lipid oxidation, color changes and volatiles production in irradiated pork sausage with di erent fat content and packaging during storage $

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1 Meat Siene 51 (1999) 355±361 Lipid oxidation, olor hanges and volatiles prodution in irradiated pork sausage with di erent fat ontent and pakaging during storage $ Abstrat C. Jo, J.I. Lee, D.U. Ahn* Department of Animal Siene, Iowa State University, Ames, IA , USA E ets of irradiation on lipid oxidation, olor and volatiles prodution in pork sausages with di erent fat ontent and pakaging were determined. Sausages (with 4.7, 10.5 and 15.8% fat ontent) were slied and vauum-pakaged either in oxygen-permeable or impermeable bags, irradiated (0 or 4.5 kgy) and stored at 4 C for 7 days. Lipid oxidation, olor and volatiles produtions were analyzed at 0, 3 and 7 days of storage. TBARS (2-thiobarbituri aid reative substanes) values of ooked pork sausages inreased with the inrease of fat ontent regardless of storage, irradiation or pakaging types. Irradiated samples had higher TBARS than nonirradiated at 0 day but the di erene disappeared during storage in both pakaging types. Lightness of sausages (Hunter L- value) inreased with the inrease of fat ontent and storage time but was not a eted by irradiation. In aerobi pakaging, irradiation redued Hunter a-values of pork sausages at 0 day but irradiation e et on a-value disappeared during storage. In vauum pakaging, however, irradiated samples had higher Hunter a-values than nonirradiated samples. Irradiation inreased 1-heptene and total volatiles, but the amount of 1-heptene was not assoiated well with TBARS values of pork sausages. In both irradiated and nonirradiated pork sausages, aerobi pakaging produed more volatiles than vauum pakaging during storage. It was onluded that irradiation and fat ontent had signi ant e ets on lipid oxidation, olor and volatiles prodution of ooked pork sausages during storage but that oxygen availability had a stronger e et than irradiation and fat ontent. # 1999 Elsevier Siene Ltd. All rights reserved. 1. Introdution Low-dose (<10 kgy) irradiation an kill at least 99.9% of salmonella in poultry and an even higher perentage of Esherihia oli 0157:H7 (Olson, 1998). But, irradiation is known to generate hydroxyl radials that an initiate hain reations of lipid oxidation in aqueous and oil emulsion systems. Irradiation ould produe a large amount of hydroxyl radials in meat beause over 75% of musle ells are omposed of water (Thakur & Singh, 1994). Thayer, Boyd, and Jenkins (1993) reported that irradiation-indued hemial hanges are dose dependent and the generation of harateristi o -odor and olor hanges in meat is almost instantaneous after irradiation. Both raw and ooked meats produe o -odor after irradiation but the soures and mehanisms of o odor prodution in irradiated meats are not yet known. * Corresponding author. Tel.: ; fax: ; duahn@iastate.edu $ Journal paper no. J of the IA Agriulture and Home Eonomis Experiment Station, Ames, Iowa , USA. Projet no. 3322, and supported by Hath At and the Food Safety Consortium. Ahn et al. (1998b) observed that aerobi-pakaged irradiated raw pork had signi antly higher TBARS values than those of ontrol. Less stable displays of olor were noted for samples irradiated in aerobi pakaging (Luhsinger et al., 1996). Akamittath, Brekke, and Shanus (1990) suggested that disoloration and lipid oxidation are interrelated and pigment oxidation may atalyze lipid oxidation. However, irradiation had no detrimental e ets on the olor or avor of ured meat with nitrite or a nitrite-free uring system. Polyphosphates had a bene ial e et on lipid oxidation but a detrimental e et on olor stability in irradiated meat (Shahidi, Pegg, & Shamsuzzaman, 1991). Lynh, Ma e, and Mead (1991) reported that irradiated turkey breast llets produed unpleasant odor notes when stored in oxygen-impermeable lm and the odor notes were di erent from those developed from orresponding nonirradiated samples. Heath, Owens, Tesh, and Hannah (1990) and Hashim, Resurreion, and MaWatters, (1995) also showed that irradiating unooked hiken meat produed a harateristi bloody and sweet aroma that remained after the meat was ooked. Reineius (1979) suggested that arbonyl ompounds are important for irradiation odor and that /99/$Ðsee front matter # 1999 Elsevier Siene Ltd. All rights reserved PII: S (98)00134-X

2 356 C. Jo et al./meat Siene 51 (1999) 355±361 Table 1 E et of fat ontent and irradiation on lipid oxidation of ooked pork sausages with di erent pakaging a Fat ontent 0 day 3 day 7 day 0 kgy 4.5 kgy SEM 0 kgy 4.5 kgy SEM 0 kgy 4.5 kgy SEM b mg Malondialdehyde equivalents/kg Meat Aerobi pakaging (%) d 3.9 d b 2.2 a b 2.2 a SEM ± ± ± Vauum pakaging (%) d d e 1.3 e d b 1.6 a d 1.6 d b 1.7 a a 1.5 b 0.05 SEM ± ± ± n=4. Di erent letters within a row are signi antly di erent ( p < 0.05). d Di erent letters within a olumn are signi antly di erent ( p < 0.05). Fig. 1. Color hanges of ooked pork sausages with aerobi pakaging during storage (&), nonirradiated pork sausage with 0% fat added; (^), nonirradiated pork sausage with 10% fat added; (*), nonirradiated pork sausage with 20% fat added; (&), irradiated pork sausage with 0% fat added; (^), irradiated pork sausage with 10% fat added; (*), irradiated pork sausage with 20% fat added). a± Di erent letters within a storage day are signi antly di erent ( p < 0.05). NonIR, nonirradiated; IR, irradiated.

3 C. Jo et al./meat Siene 51 (1999) 355± Fig. 2. Color hanges of ooked pork sausages with vauum pakaging during storage (&), nonirradiated pork sausage with 0% fat added; (^), nonirradiated pork sausage with 10% fat added; (*), nonirradiated pork sausage with 20% fat added; (&), irradiated pork sausage with 0% fat added; (^), irradiated pork sausage with 10% fat added; (*), irradiated pork sausage with 20% fat added). a± Di erent letters within a storage day are signi antly di erent ( p < 0.05). NonIR, nonirradiated; IR, irradiated. Table 2 E et of fat ontent on the prodution of volatiles in irradiated aerobi-pakaged pork sausages after 0 day of storage at 4 C a Volatiles Nonirradiated Irradiated 4.7% 10.5% 15.8% SEM b 4.7% 10.5% 15.8% SEM 1-heptene 1.0 b 5.6 a 9.0 a Propanal b 17.6 a b 26.0 a methylpropanal methylbutanal Pentanal pentanone 98.6 a 81.7 ab 54.5 b a 61.8 b 47.2 b 11.9 Hexanal a ab b butanol pentanol a 14.8 a 10.1 b 1.0 Nonanal a 3.3 b 1.0 b 0.8 Deanal nd d nd nd 0.8 nd nd heptanol Aldehydes + ketones a b b 19.3 Alohols a 22.3 a 15.4 b 1.6 Total volatiles a b b 22.6 Di erent letters within a row are signi antly di erent ( p < 0.05). n =12. d nd: n=not deteted.

4 358 C. Jo et al./meat Siene 51 (1999) 355±361 the intensity of irradiation odor is dependent upon oxygen ontent during irradiation. El Magoli, Laroia, and Hansen (1996) indiated that 2-butanone, 2-pentanone and 3-hydroxy-2-butanone inreased with the inrease of fat ontent from 11 to 22% in beef patties, and Ahn et al. (1998b) reported that propanal, pentanal, hexanal, 1-pentanol and total volatiles orrelated highly ( p < 0.01) with TBARS values of ooked meat. Although lipid is the most important substane for quality hanges in meat, the e et of fat ontent on the development of lipid oxidation, olor hanges and volatiles prodution in irradiated meat is limited. The objetive of the present researh was to determine the in uene of irradiation on lipid oxidation, olor hange and volatile prodution in ooked pork sausages with di erent fat ontent and pakaging during storage. 2. Materials and methods 2.1. Sample preparation Lean pork was obtained from a loal paker and ground twie through a 9-mm plate. Pork sausages batters were prepared with the lean ground meat, bak fat (0, 10 or 20% of meat weight), NaCl (2%) and ie water (10%). The batters were stu ed into ellulose asings (3 m thikness) and ooked in a smoking hamber to an internal temperature of 72 C. After ooling by a old water shower, the sausages were slied to 2 m-thik piees (approximately 30 g), vauum-pakaged into oxygen-impermeable nylon/polyethylene bags (9.3 ml O 2 /m 2 /24 h at 0 C; Koh, Kansas City, MO) and stored in a 4 C refrigerator overnight. Irradiation was onduted the next day at 0 or 4.5 kgy dose (97 kgy/min) using a Linear Aelerator (Cire IIIR, Thomson CSF Lina, Frane). For the aerobi pakaging treatment, vauum pakaging bags were opened before irradiation. Samples were stored in a 4 C refrigerator immediately after irradiation and 0-day samples were analyzed 3 h after storage Measurements of lipid oxidation, olor and fat ontent Lipid oxidation was determined using a spetrophotometer (Gilford Instrument Laboratories, Oberlin, OH) as desribed in detail by Jo and Ahn (1998a). TBARS values were expressed as mg malondialdehyde (MDA) equivalents per kg meat. A CIE Lab olor [lightness (L), redness (a) and yellowness (b)] of sausages was measured using a Hunter Colorimeter (Hunter Assoiates Laboratories, Reston, VA). Total fat ontent was determined by the Folh's extration method (Folh, Less, & Sloane-Stanley, 1957) Volatiles analysis Preept II and a Purge-and-Trap onentrator (Model 3000, Tekmar-Dohrmann, Cininnati, OH) were used to purge and trap volatiles, and a gas hromatography (GC) (Hewlett Pakard, Model 6890, Wilmington, DE) equipped with a ame ionization detetor (FID) was used to analyze volatiles from pork sausages. Table 3 E et of fat ontent on the prodution of volatiles in irradiated vauum-pakaged pork sausages after 0 day of storage at 4 C a Volatiles Non irradiated Irradiated 4.7% 10.5% 15.8% SEM b 4.7% 10.5% 15.8% SEM b 1-heptene Propanal b 22.2 a 23.9 a methylpropanal methylbutanal Pentanal b 33.6 a 32.7 a pentanone Hexanal a b b butanol pentanol a 12.6 ab 11.1 b 0.7 Nonanal a 1.0 b 1.0 b 0.1 Deanal nd d nd nd nd nd nd 1-heptanol nd nd nd Aldehydes + ketones a ab b 20.1 Alohols a 18.2 ab 14.0 b 2.0 Total volatiles b a ab a ab b 21.3 Di erent letters within a row are signi antly di erent ( p < 0.05). n=12. d nd: not deteted.

5 C. Jo et al./meat Siene 51 (1999) 355± Meat (2 g) was sampled into a vial (40 ml) and analyzed using the onditions desribed in detail by Ahn et al. (1998a). The area of eah peak was integrated and reported as an indiator of volatiles generated from the meat samples Statistial analysis Experimental design was onstruted to determine the e et of irradiation and fat ontent on lipid oxidation, olor hanges and volatile prodution in ooked sausages stored in two pakaging onditions. Analyses of variane (SAS Institute, 1988) were used to nd di erenes and the Student±Newman±Keul's multiple range test was used to ompare di erenes among mean values. Mean values and standard errors of the mean (SEM) were reported. 3. Results and disussion 3.1. Lipid oxidation Regardless of storage time, irradiation or pakaging types, TBARS values in sausages inreased with the inrease of fat ontent (Table 1). Fat ontent of sausages prepared with 0, 10 and 20% bakfat added were 4.7, 10.5 and 15.8%, respetively. Irradiation inreased the lipid oxidation of sausages with 10.5 and 15.8% fat ontent in both aerobi and vauum pakaging at day 0. However, the irradiation e et on lipid oxidation disappeared during storage exept for the sausages with 15.8% fat ontent in vauum pakaging. The TBARS values of vauum-pakaged pork sausages were very similar throughout storage indiating that oxygen availability is the most ritial fator in the development of lipid oxidation Color Irradiation had no e et on Hunter L-values of sausages both with aerobi and vauum pakagings (Figs. 1 and 2). Pork sausages with high fat produed lighter olor than low-fat sausages. Storage inreased Hunter L-values of pork sausages with both pakagings but, the hanges of Hunter L-values in vauum-pakaged sausages were smaller than those of the aerobi-pakaged. Irradiation redued a-values of aerobi-pakaged pork sausages at day 0 but had no e et on those at day 3. Nonirradiated pork sausages with 10% bakfat added had higher a-value than that of the irradiated sausages with 20% bakfat added at day 7. However, there were no di erenes in a-values between irradiated and nonirradiated sausages within a same bakfat treatment at day 7. The Hunter a-values of aerobi-pakaged pork sausage gradually dereased in all treatments as storage time inreased. The a-values of all pork sausage were the highest in vauum-pakaged irradiated sausages and the lowest in aerobi-pakaged nonirradiated sausages. Therefore, pakaging type (oxygen availability) was again an important fator for maintaining the olor of slied pork sausages during storage. Irradiation redued Hunter b-values of vauum-pakaged sausages but had no e et on Hunter b-values of the aerobi-pakaged produt. Table 4 E et of fat ontent on the prodution of volatiles in irradiated aerobi-pakaged pork sausages after 7 days of storage at 4 C a Volatiles Nonirradiated Irradiated 4.7% 10.5% 15.8% SEM b 4.7% 10.5% 15.8% SEM b 1-heptene a 21.3 b 55.3 a 2.6 Propanal b a methylpropanal a 89.8 b methylbutanal a 18.1 b 24.9 a 1.0 Pentanal 33.3 a 26.9 a 20.1 b a 18.9 b 35.6 a pentanone Hexanal a b b a b b butanol pentanol 29.8 a 25.3 a 21.5 b a 18.1 b 15.0 b 1.1 Nonanal 7.0 a 3.8 b a 3.6 b 2.9 b 0.3 Deanal a 0.3 b nd d heptanol 6.8 a 4.3 b a 3.2 b Aldehydes + ketones a b b a b b 25.2 Alohols 41.8 a 37.1 b a 29.0 b Total Volatiles a b b a b b 27.1 Di erent letters with in a row are signi antly di erent ( p < 0.05). n=12. d nd: not deteted.

6 360 C. Jo et al./meat Siene 51 (1999) 355± Volatiles High-fat sausages produed more propanal but less 1- pentanol, nonanal and 1-heptanol than low-fat produts (Tables 2±5). The amounts of aldehydes, ketones and alohols were the highest in pork sausages with 4.5% fat and the lowest in sausages with 15.8% fat. Among individual volatile ompounds, only propanal showed the same trend as TBARS values, whih inreased with the inrease of fat ontent (Table 1). This indiated that there would be ertain interations between fat ontent and prodution of volatiles in pork sausages. Reently, Ahn et al. (1998b) reported that ooked pork patties from L. dorsi, whih had about 2.5 to 3 times higher fat ontent than those from R. fermoris, produed less hexanal and total volatiles than those from R. fermoris at the same TBARS value. Jo and Ahn (1998b) on rmed this trend using an oil emulsion study. Their results suggested that if the amount of volatiles is used as an indiator of lipid oxidation or o - avor generation in ooked pork produts, the fat ontent of samples should be taken into onsideration. Irradiation inreased the amount of 1-heptene in pork sausages signi antly but storage or pakaging type did not (Tables 2±5). Although very small amounts of 1-heptene were found in nonirradiated pork sausages, 1-heptene was an exellent indiator for irradiation treatments. Villavienio, Manini-Filho, Hartmann, Ammon, and Delinee (1997) suggested the use of hydroarbons to detet radiation treatment in the proessing of beans. Nawar et al. (1996) reported that irradiation breaks hemial bonds in triaylglyerides and produes arbonyl ompounds suh as C n 1 and C n 2:1 hydroarbons. The C n 1 has one arbon atom less than the parent fatty aid, and the C n 2:1 has a double bond in position 1 and is two arbon atoms less than the parent fatty aid. Therefore, 1-heptene (C7:1) would be a produt from nonane (C9:0) that oxidized and leaved from olei or other n 9 fatty aids during irradiation and storage. The produtions of nonanal, deanal or 1- heptanol in vauum-pakaged pork sausages (both irradiated and nonirradiated) were very small. The amount of total volatiles in irradiated ooked pork produts was signi antly higher than the amount in the nonirradiated produts. In addition to the amount of identi ed volatiles, many unknown volatiles with short retention time also were found in irradiated samples. This means that irradiation inreased not only volatiles prodution but also the number of volatile ompounds. Most probably, these volatiles would be nonpolar small hydroarbons and ould be important for irradiation odor but were exluded from the alulation of total volatiles. More volatiles were produed as the development of lipid oxidation in pork sausages progressed during storage (Tables 2±5). Shahidi and Pegg (1994) observed that the ontent of hexanal, an index of lipid oxidation and meat avor deterioration, delined markedly upon extended storage of meat. They indiated that the reations of hexanal with meat omponents or its further oxidation to hexanoi aid were responsible for the redution of hexanal in meat during storage. The present study showed derease of hexanal in pork sausages after 7-day storage only in vauum pakaging. The reason for hexanal hange in vauum-pakaged pork sausages during storage annot be explained. Table 5 E et of fat ontent on the prodution of volatiles in irradiated vauum-pakaged pork sausages after 7 days of storage at 4 C a Volatiles Nonirradiated Irradiated 4.7% 10.5% 15.8% SEM b 4.7% 10.5% 15.8% SEM b 1-heptene 5.3 b 6.9 ab 9.1 a Propanal b 15.1 a b 16.8 a 20.1 a methylpropanal methylbutanal a 36.3 b 1.9 Pentanal b 29.5 a 30.6 a pentanone Hexanal a ab b butanol pentanol a 10.9 a Nonanal nd ab 1.7 ab 1.2 b 0.2 Deanal nd d nd nd nd nd nd 1-heptanol nd a 1.0 a 0.3 b 0.2 Aldehydes + ketones Alohols b 18.7 a Total volatiles Di erent letters within a row are signi antly di erent ( p < 0.05). n=12. d nd: not deteted.

7 C. Jo et al./meat Siene 51 (1999) 355± Ahn et al. (1998b) observed that oxygen exlusion from meat after ooking was more important in preventing lipid oxidation of ooked meat than raw meat treatments. The authors reported that lipid oxidation was not atalyzed by the ooking proess but by subsequent oxygen ontat with ooked meat during storage. Pakaging types had the most in uene on the prodution of volatiles, lipid oxidation and olor hanges in ooked pork sausages during storage. It was onluded that keeping oxygen from meat was more important than irradiation and fat ontent in maintaining a high quality of meat after ooking. Referenes Ahn, D. U., Olson, D. G., Jo, C., Chen, X., Wu, C., & Lee, J. I. (1998). E et of musle type, pakaging, and irradiation on lipid oxidation, volatile prodution, and olor in raw pork patties. Meat Siene, 49, 27±39. Ahn, D. U., Olson, D. G., Lee, J. I., Jo, C., Wu, C., & Chen, X. (1998). Pakaging and irradiation e ets on lipid oxidation and volatiles in pork patties. Journal of Food Siene, 63, 15±19. Akamittath, J. G., Brekke, C. J., & Shanus, E. G. (1990). Lipid oxidation and olor stability in restrutured meat systems during frozen storage. Journal of Food Siene, 55, 1513±1517. El Magoli, S. B., Laroia, S., & Hansen, P. M. T. (1996). Flavor and texture harateristis of low fat ground beef patties formulated with whey protein onentrate. Meat Siene, 42, 179±193. Folh, J., Less, M., & Sloane-Stanley, G. M. (1957). A simple method for the isolation and puri ation of total lipids from animal tissues. Journal of Biologial Chemistry, 226, 497±509. Hashim, I. B., Resurreion, A. V. A., & MaWatters, K. H. (1995). Disruptive sensory analysis of irradiated frozen or refrigerated hiken. Journal of Food Siene, 60, 664±666. Heath, J. L., Owens, S. L., Tesh, S., & Hannah, K. W. (1990). E et of high-energy eletron irradiation of hiken on thiobarbituri aid values, shear values, odor, and ook yield. Poultry Siene, 69, 313±319. Jo, C., & Ahn, D. U. (1998). Fluorometri analysis of 2-thiobarbituri aid reative substanes in turkey. Poultry Siene, 77, 475± 480. Jo, C., & Ahn, D. U. (1998b). Fat redues volatiles prodution in oil emulsion system analyzed by purge-and-trap dynami headspae/ gas hromatography (unpublished). Luhsinger, S. E., Kropf, D. H., Garia-Zepeda, C. M., Hunt, M. C., Marsden, J. L., Rubio Canas, E. J., Kastner, C. L., Kueker, W. G., & Mata, T. (1996). Color and oxidative ranidity of gamma and eletron bean-irradiated boneless pork hops. Journal of Food Siene, 61, 1000±1004, Lynh, J. A., Ma e, H. J. H., & Mead, G. C. (1991). E et of irradiation and pakaging type on sensory quality of hill-stored turkey breast llets. International Journal of Food Siene and Tehnology, 26, 653±668. Nawar, W. W., Zhu, Z., Wan, H., Degroote, E., Chen, Y., & Aiukewiz, T. (1996). Progress in the detetion of irradiated food by measurement of lipid derived volatiles. In: C. H., MMurray, E. M. Stewart, R. Gray, J. Peare (Eds.), Detetion methods for irradiated foods (pp. 241±249). Cambridge: Royal Soiety of Chemistry. Olson, D. G. (1998). Irradiation of food. Food Tehnology, 52, 56±62. Reineius, G. A. (1979). Symposium on meat avor. O - avors in meat and sh ± A review. Journal of Food Siene, 44, 12±21. SAS Institute. (1988). SAS user's guide 1. Cary, NC: SAS Institute. Shahidi, F., Pegg, R. B., & Shamsuzzaman, K. (1991). Color and oxidative stability of nitrite-free ured meat after gamma irradiation. Journal of Food Siene, 56, 1450±1452. Shahidi, F., & Pegg, R. B. (1994). Hexanal as an indiator of the avor deterioration of meat and meat produts. Amerian Chemial Soiety Symposium Series, 558, 256±279. Thakur, B. R., & Singh, R. K. (1994). Food irradiation. Chemistry and appliations. Food Review International, 10(4), 437±473. Thayer, D. W., Boyd, G., & Jenkins, R. K. (1993). Low-dose gamma irradiation and refrigerated storage in vauum a et mirobial ora of fresh pork. Journal of Food Siene, 58, 717±719, 733. Villavienio, A. C. H., Manini-Filho, J., Hartmann, M., Ammon, J., & Delinee, H. (1997). Formation of hydroarbons in irradiated Brazilian beans: Gas hromatographi analysis to detet radiation proessing. Journal of Agriultural and Food Chemistry, 45, 4215± 4220.

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