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Yasemin Yildirim · M ¨uge ˙Inu˘gur Spoilage and shelf life of sardines Sardina pilchardus packed in modified atmosphere Received: 4 August 2005 / Revised: 26 October 2005 / Accepted: 31

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DOI 10.1007/s00217-005-0194-8

O R I G I NA L PA P E R

Nuray Erkan · ¨Ozkan ¨Ozden ·

Didem ¨ Uc¸ok Alakavuk · S¸ Yasemin Yildirim ·

M ¨uge ˙Inu˘gur

Spoilage and shelf life of sardines (Sardina pilchardus) packed

in modified atmosphere

Received: 4 August 2005 / Revised: 26 October 2005 / Accepted: 31 October 2005 / Published online: 16 December 2006

C

 Springer-Verlag 2005

Abstract The effect of modified atmosphere packing

(%)) on the quality of sardine stored in refrigerator was

investigated in terms of sensory, chemical and

microbio-logical analysis Although chemical and microbiomicrobio-logical

analyses indicated that modified atmosphere packing

pro-longed the shelf life of sardine compared with that of air

packing, sensory analysis showed that the extension of shelf

air and MAP storage conditions

Keywords Sardine Modified atmosphere packing

Shelf life Fish quality

Introduction

Storage of fish products on ice under modified atmosphere

packing (MAP) prolongs the shelf life for some days

This is becoming a very favorable alternative for fresh fish

preservation [1] The shelf life of fresh fish is limited by

the growth and biochemical activities of Gram-negative,

psychrotrophic strains of Pseudomonas, Achromabacter,

Flavobacterium and Moraxellla species in the presence of

by packaging of products in an impermeable film under a

con-ditions, the growth of common spoilage microorganisms

is inhibited and microaerophilic strains of lactic acid

bac-teria become the dominant spoilage microorganisms As

a result of the inhibition of spoilage microorganisms,

lev-els of chemical compounds, for example, trimethylamine

N Erkan ( ) · ¨O ¨Ozden · D ¨U Alakavuk · S¸ Y Yildirim ·

M ˙Inu˘gur

Istanbul University, Faculty of Fisheries, Department of the

Seafood Processing and Quality Control,

Ordu Cad No.: 200 34470 Laleli/Istanbul, Turkey

e-mail: nurerkan@istanbul.edu.tr

(TMA), total volatile nitrogen (TVB-N), which are chem-ical indicators of microbial spoilage of food, are also re-duced [3] Many reports have observed that the shelf life

indirectly responsible for the quality deterioration of fish They involve lipolysis, lipid oxidation, and interaction of the products of these processes with nonlipid components such as protein Lipid oxidation takes place mostly in fatty fishes These fishes contain more free lipids and more dark muscles compared to the white muscles The oxidation of the tissue lipids has a very large effect on the quality of fish [7] Lipid deterioration limits shelf life of oily fish such as

gly-colipids and phospholipids are hydrolyzed by lipases to free fatty acids, which then undergo further oxidation to produce low molecular weight compounds, such as alde-hydes and ketones These compounds are responsible for off-flavor, off-odour, and taste of fish [3] Ruiz-Capillas

shelf life of fish products in MAP can be extended, de-pending on raw materials, temperature, gas mixtures, and packaging materials [11] Thus the objective of this study was to determine the effect of MAP storage on the shelf

life of sardine (Sardine pilchardus) by monitoring sensory,

chemical, and microbiological changes throughout

Materials and methods

Fresh sardine (Sardina pilchardus) which is a pelagic

Mar-mara Sea species was obtained from a fishing port Fresh fish in wooden boxes with ice was transported to the lab-oratory in 6 h Twenty kilograms samples were used for the experiment The fishes were ungutted These fishes were individually beheaded, gutted, and washed They were washed once, with tap water after landing Gutting

of the fishes was carried out manually in the fish process-ing plant and were divided into three lots The sardines

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placed in high-barrier plastic film bags (UPM-Kymmene,

Walki-Pack, Plastic Films Factory (Valkeakoski, Finland)

The characteristics of the plastic film bags were as follows:

90±2% RH g/m2days atm Control samples were packaged

under atmospheric conditions Gas packed in a Henkovac

model E-173, vacuum-packaging machine (Switzerland)

de-terminations were done by triplicate at days 1, 3, 5, 7

and 9

Sensory assessment

The cooked white fishes were assessed using the simplified

Torry Sensory Scheme [12] Panelists were asked to score

odor, taste and texture of fish using a 0–10 acceptability

6= ‘good’, 5.9–4 =‘sufficient’, 4 = ‘limit of acceptable’,

≤3 = ‘unacceptable’.

Chemical analysis

Measurement of pH

Aliquots of 10 sardines were filleted from each sampling

lot and homogenized using a food processor Samples were

prepared according to Manthey et al [13] by blending 5 g of

the homogenate with 10 ml distilled water for 1 min at room

temperature in an Ultra-Turrax (IKA T 25 Basic, Germany)

pH was monitored using a WTW pH Meter (InoLab pH

Level 1 model, Weilheim, Germany) Determinations were

carried out in triplicate at days 1, 3, 5, 7 and 9 during the

storage period

Determination of total volatile basic nitrogen (TVB-N)

Total volatile basic nitrogen was determined according to

the Antonacopoulos and Vyncke, [14] method For total

volatile basic nitrogen, fish muscle (10 g) was

homoge-nized with 6% perchloric acid (90 ml) for 1 min in an

Ultra-Turrax (IKA T 25 Basic, Staufen, Germany) The

homogenates were filtered through a filter paper

(What-man No 1) and filtrates alkalized by NaOH (20%), before

distillation duplicate filtrates were distilled in a Velp Marka

model UDK 140, Milano, ˙Italy apparatus The distillate was

titrated with 0.01 N HCl

Determination of trimethylamin nitrogen (TMA-N)

This was determined by the method of AOAC, [15] Ten

grams homogenized samples were weighed, blended with

90 ml of 7.5% trichloracetic acid solution and filtrated

Blended solution was fixed with formaldehyde (20%) Four milliliters extract was transferred into test tubes and 1 ml

solution were added The tubes were shaken and 5 ml toluene layer was pipetted Five milliliters picric acid work-ing solution (0.02%) was added The contents were mixed and transferred to a spectrophotometric cell Absorbance at

410 nm against the blank was measured At the same time, standards were prepared and measured Results of TVB-N

and TMA-N were expressed as mg/100 g muscle The P

value was calculated according to the following expression [16]

P(%)= TMA− N

TVB− N × 100

Determination of lipid oxidation

The distillation method of Tarladgis et al [17] as modified

by Witte et al [18] was used to determine the degree of lipid oxidation in meat samples Lipid oxidation is mea-sured using tiobarbituric acid (TBA values), which were expressed in mg malonaldehyde/kg meat Malonaldehyde was a breakdown product of lipid oxidation Peroxid value (PV) was determined by a titrimetric Wheeler method [19] after fat extraction [20]

Determination of histamine

Histamine content was determined in triplicate by the en-zyme linked- immunosorbent assay (ELISA) methods [21] with commercial rapid histamine test kits (Veratox his-tamine test kits from Neogen, Lansing, USA and Canada) Results were read using a micro well reader (Neogen Stat Fax 303) with a 650 nm filter

Microbiological analyses Samples (25 g) were mixed with 225 ml of pepton wa-ter (Merck, Kat No.: 107228) diluents in a Stomacher (Stomacher, IUL Instrument, Spain) Further serial dilu-tions were made in tubes before plating The media and incubations were: for mesophilic aerobic plate count PCA

for psychrotrophic bacteria PCA agar (PCA, Merck, Kat

putrefaciens) Iron agar 25 ◦C, 2 days [24]; and for

En-terobacteriaceae VRGB agar (Merck, Kat No.: 110275)

colony forming units (log CFU) per gram of sample Sul-fite reducing Clostridias were determined in Differential Reinforced Clostridial Broth (Merck, 111699) after

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(MPN, 3 tubes/dilution) method Results were expressed as

log MPN/g of samples Anaerob Clostridias were

investi-gated in the same way, except that an anaerobic atmosphere

kit (Merck, 113829) was placed, together with the plates,

inside the anaerobiosis jar (Merck, 116387) [25]

Statistical analysis

Significant differences between the samples were

calcu-lated by Excel XP 2003 by one-way analysis of variance

Honestly Significant Difference test Pearson’s regression

analysis was performed to determine the correlation

be-tween analyses [26]

Results and discussion

Sensory analysis

Sensory scores of air and MAP packaged sardines

cor-responding limit for taste and odor was reached after 5 days

for control and group A samples, after 7 days for B group

to the species, the initial microbial flora, area of catch,

the method of catching, processing method, and storage

method Pacheco-Aguilar et al [27] Nunes et al [28],

re-ported that the limit of acceptability for whole sardine was

5 days Ozden and G¨oko˘glu [29] concluded that the shelf

life of gutted sardine in refrigerator is extremely limited,

typical 6 days after catch whereas Gennari et al [30]

re-ported that organoleptic rejection of the whole sardine was

reached at 8 days in ice storage The storage life of fish

is affected by the initial microbial load of the fish, storage

temperature, and packing methods This long shelf life of

fish was achieved due to the maintenance of chilled

temper-ature at harvest and during the storage of packing materials

This result is in agreement with those of Dhananjaya and

(60/40) gas mixture on the storage life of herring This

author reported that the stored MAP herring was still

ac-ceptable after 14 days, although the control sample was

barely acceptable after 12 days of storage Storage life

13 days, while air-packaged tilapia has a storage life of

12 days; in vacuum, 9 days and 3 days in air

Chemical analysis

At the beginning of the storage, the pH value was 6.02– 6.03 and 6.03 for sardine in air and MAP The pH val-ues increased to 6.20 by the end of the storage period for sardine packed in air and 6.21 and 6.23 for sardine packed in MAP Values of pH showed statistically

during the entire period of storage The pH increases were

in agreement with the findings of Manthey et al [13], El Marrakchi et al [33] and Nunes et al [28] for other fish species stored in ice During the storage period, the pH value increased according to the storage time, but the pH value is not a criterion of spoilage It has to be supported

by other chemical and sensory analyses [34] The pH of live fish muscle is close to the value 7.0 However, chilled fish pH can vary from 6.0 to 6.5 depending on fish species and other factors [35] In fish, refrigerated in aerobic con-ditions, the rise in pH is mainly due to the production of trimethylamine and other volatile bases due to the spoilage

by bacteria Growth of these species and therefore, gener-ation of trimethylamine and volatile bases were inhibited when samples were stored in carbon dioxide enriched at-mospheres producing a drop in pH [36] Sardine muscle

pH decreases rapidly during postmortem The pH of MAP packaged fish were not good indicators of spoilage [6] The TVB-N content in muscle increased in the period between the first and 9th days of storage in the control and MAP groups Finally, average TVB-N values as

18.19 mg/100 g were determined in groups A and B and

in control groups, respectively after 9 days of storage The TVB-N limit of acceptability (35 mg/100 g) for consump-tion of fish for hake steaks have been reported by Ord´onez

et al [36] as 7 days of storage in air, 11 days when packaged

Table 1 Changes in sensory

analyses in sardine during the

period of iced storage

Texture score of cooked fish

C 9.1±0.1 8.8±0.01 7.8±0.01 5.2±0.1 4.0±0.42

A 9.2 ±0.2 8.7 ±0.2 7.9 ±0.01 5.1 ±0.1 4.0 ±0.33

B 9.1±0.3 8.8±0.01 7.9±0.01 5.2±0.1 4.2±0.20 Odor score of

cooked fish

C 8.9 ±0.5 7.1 ±0.1 5.9 ±0.01 2.8 ±0.2 2.1 ±0.2

B 8.9 ±0.2 7.5 ±0.25 6.12 ±0.3 3.6 ±0.2 2.8 ±0.1 Flavor score of

cooked fish

A 8.9 ±0.6 7.6 ±.0.24 4.2 ±0.1 2.9 ±0.01 2.2 ±0.3

B 9.1±0.4 7.75±0.01 5.1±0.2 4.2±0.01 2.95±0.25 C: control group; A: group A;

B: group B

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Table 2 Changes in chemical analyses in sardine during the period of iced storage

pH C 6.01 ±0.01 6.06 ±0.003 6.17 ±0.003 6.15 ±0.01 6.20 ±0.02

A 6.03 ±0.003 6.03 ±0.01 6.16 ±0.01 6.12 ±0.003 6.21 ±0.003

TVB-N (mg/100 g muscle) C 10.64 ±0.11 21.31 ±0.09 23.44 ±0.43 26.46 ±0.5 18.19 ±0.19

A 10.60±0.28 20.45±0.52 21.69±0.10 25.41±0.15 36.08±1.3

B 10.88 ±0.16 20.57 ±0.13 24.81 ±0.40 24.4 ±0.38 35.5 ±1.15 TMA-N (mg/100 g muscle) C 2.38±0.03 2.32±0.07 4.11±0.03 6.82±0.08 7.74±0.53

A 2.41 ±0.09 2.61 ±0.05 5.64 ±0.19 6.82 ±0.08 9.69 ±0.25

A 22.73±0.15 12.76±0.09 26.0±0.15 26.84±0.10 26.86±0.07

B 22.61 ±0.10 10.69 ±0.07 13.10 ±0.20 15.41 ±0.45 20.59 ±0.56

A 12.30 ±0.03 26.29 ±0.02 52.56 ±0.02 34.42 ±0.03 52.86 ±0.02

B 12.30±0.04 22.56±0.04 25.94±0.02 23.57±0.04 45.26±0.02

PV (mmol O2/kg) C 2.90 ±0.01 7.28 ±0.02 9.97 ±0.07 10.29 ±0.2 12.11 ±0.28

B 3.60 ±0.03 3.46 ±0.22 7.58 ±0.02 9.70 ±0.35 9.93 ±0.3 TBA (mg malonaldehyde/kg) C 1.02±0.01 5.49±0.03 6.62±0.25 6.43±0.4 7.31±0.03

A 1.08 ±0.07 3.45 ±0.09 7.42 ±0.18 6.98 ±0.1 4.53 ±0.01

C: control group; A: group A; B: group B

TMA are products of bacterial spoilage and their contents

are often used as an index to assess the keeping quality and

the shelf life of seafood products Higher TVB-N values

in the range 25–35 mg/100 g indicate that the fishes were

slightly decomposed/edible and decomposed/inedible

con-centration of TVB-N never reaches 20 mg/100 g in many

fatty fishes [39]

The pattern of increase in the TMA-N value from day

0 to day 9, for sardines kept under three different packing

TMA-N values is fairly linear with storage time in three

level of TMA-N between sardine held in air and in group

A and particularly in groups B (7 days) The observed

shelf life of sardines was found to be 9 days (TMA-N

value, 7 mg/100 g) in group B, 7 days (TMA-N value,

6.82 mg/100 g) in group A and for fish stored in air Initial

P values under air and MAP packaged sardines were 22.36,

22.73 and 22.61%, respectively The value of P increased

and its level reached more than 42.55% for air treatment,

26.86% for group A and 20.59% for group B

Initial values of TMA in muscle from these values

agreed with Morocco sardine [33], for mackerel [40],

and for herring [41] In the postmortem animal, enzymes

from spoilage microorganisms primarily metabolize the

extractive fraction of the fish muscle, producing a wide

variety of volatile compounds resulting in off-flavors and

odors [42] Trimethylamine oxide (TMAO), found in a

large number of marine fish and shellfish, is broken down to

trimethylamine (TMA) either by the endogenous enzymes

The quantitative level of TMA in fish is considered a major index of the quality of marine fish [44] The rejection limit is usually 5–10 mg TMA-N/100 g muscle; however,

in numerous fatty fishes the concentration of TMA-N never reaches the limit of 5 mg TMA-N/100 g [39] Ababouch et al [38] reported similar levels of TMA-N (5–10 mg/100 g) of sardine El Marrakchi et al [33] proposed that TMA-N levels for first grade, second grade,

muscle of fish sample, respectively G¨oko˘glu et al [45]

TMA-N levels at day 0 and 10 were 1.45 and 10.1 mg TMA-N/100 g muscle, respectively The level of TMA was typically around 10–15 mg/100 g, in aerobically stored fresh fish, rejected by sensory panels [46] The concentration of TMA was found to be 13.5 mg in herring

of TMA sardines in air, followed by sardines stored in vacuum packed and the lowest in MAP with the same

trimethylamine production in MAP-cod, but it is on the

results have been reported by Hoz et al [49] and Ord´onez

et al [36] for salmon steak and hake slices under carbon dioxide enriched atmospheric conditions with TMA con-tent lower than that of air conditions Pastoriza et al [50]

TMA-N value of tilapia, 0.07 mg/100 g This value

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increased to 2.59 mg/100 g after 9 days (rejection time) of

storage in air packed samples and 1.83 mg/100 g after 13

Biogenic amines are formed in foods by the bacterial

and enzymatic decarboxylation of free amino acids They

are of great importance from the point of food intoxication

and also as chemical indicators of spoilage Histamine, a

biogenic amine, is rarely found in fresh fish, but its level

increases with the progress of fish decomposition

Infor-mation is presently available only on the production of

histamine and other biogenic amines in fish such as tuna,

mackerel, sardine, horse mackerel, anchovy, mahi-mahi,

and flying fish [52] A biogenic amine level has been

pro-posed as another way for assessing fish hygienic quality

[53] Histamine value increased after day 3 of storage in the

samples kept in air and MAP In these samples, a histamine

value of approximately 46 ppm after 5 days of storage was

recorded, close to the value of decomposed limit (50 ppm)

for fish in FDA In samples, stored in modified atmospheres,

these bases were produced at a slower rate reaching a value

close to 52 and 45 ppm by 9th day in sardine packaged

respectively Jhaveri et al [54] found initial histamine level

of 20 ppm in Atlantic mackerel They also stated that the

levels increased to value of 100 ppm in 15 days in ice El

Marrakchi et al [33] reported that the amount of histamine

in sardine flesh at the time of rejection (12 days) in ice was

162 ppm Pacheco-Aguilar et al [27] found a very small

amount of histamine (1.8 ppm) in Monterey sardine

mus-cle in ice The content of histamine sardine stored in air

day of sensory acceptability At the time of rejection, the

contents of histamine in herring and mackerel stored in VP

[49] reported that histamine in salmon steaks, at the time

(40/60)) Ord´onez et al [36] found that histamine

concen-tration increased during refrigerated storage of hake steaks

(40/60)) 8.46 ppm Histamine is a chemical hazard

moni-tored by the Food and Drug Administration of the USA for

the safety of seafood products Current FDA [56] guidelines

have established histamine levels of 200 ppm as indicative

of contamination in tuna, 500 ppm as indication of serious

health hazard and lately defined a new hazard action

The increase in PV, which is considered as the starting

point of spoilage, began on day 3 in the control, on days

and 5 mg malonaldehyde/kg TBA value is taken as a limit

of acceptability for consumption of fish, air and in the

a shelf life of 3 days, whereas it would be extended up to 5

atmo-sphere The effect of autolytic enzymes on seafood spoilage

resulting from hydroperoxide formation has been discussed

already However, there are other types of spoilage related

to hydroperoxide formation that are nonenzymatic, namely, oxidative rancidity and nonenzymatic browning These are mainly due to chemical changes in muscle tissues as a re-sult of a wide range of factors, particularly the nature of the lipids Oxidative rancidity has been long recognized as a major cause of seafood and food spoilage The process in-volves oxidation of unsaturated fatty acids or triglycerides

in seafood [3] Factors that may influence lipid oxidation, and thus seafood spoilage, include free radical mechanism, various biochemical substances, temperature, water activ-ity, pH, and chemical environment [57] The primary prod-uct of lipid oxidation is fatty acid hydroperoxide, measured

as peroxide value TBA value measured as secondary prod-uct of lipid oxidation TBA consists mainly of malondialde-hyde as representative of aldemalondialde-hydes [9] Ludorff and Meyer, [34] proposed the following Peroxide value (PV) scale as a

good’, PV =2–5 ‘good’, pH=5–8 ‘acceptable’, pH=8–10

G¨oko˘glu, [8] correlated sensory evaluation with oxidation

malonaldehyde/kg muscle for incipient and moderate ox-idation, respectively TBA index is widely used indicator for the assessment of degree of lipid oxidation [59] It was suggested that a maximum level of TBA value indicating the good quality of the fish frozen, chilled or stored with ice is 5 mg Malonaldehyde/kg [28]

Microbiological analysis There was an initial lag phase with no significant growth

of all microorganisms (aerobic, psychrotrophic, sulphide producing bacteria, Enterobacteria and sulphide reducing

3 and 5 After 5 days in control group samples there were no further significant increases in surface counts

(p <0.05) showing that the stationary phase in bacterial

growth had been attained The results of microbiological analysis showed that fish started to spoil after 5 days be-cause of bacterial activity

to delay spoilage of fresh seafood by inhibiting psy-chrotrophic, aerobic, and Gram-negative bacteria [5] Ini-tial bacterial population, gas/fish ratio, and packaging ma-terials are important factors affecting the shelf life of fish in packages [60] Gobantes et al [61] have accepted the

industry generally considers spoilage to occur when the

refriger-ated squid, the microbial limit of acceptability is

et al [64] reported that mesophilic aerobic counts showed

a slight increase for redfish during storage, reaching a value

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Table 3 Changes in microbiological analyses in sardine during the

period of iced storage

Psychrotrophic

bacteria count

(log cfu/g)

Total aerob mesophilic

bacteria count

(log cfu/g)

C 3 3.30 3.95 3.70 3.70

H2S-producing

bacteria counts

(log cfu/g)

C 3 3.47 4.70 4.18 3.70

Enterobacteriaceae

(log cfu/g)

Pseudomonas spp

(log cfu/g)

Sulphide reducing

Clostridia’s

(log MPN/g

C 0.47 0.47 0.56 1.63 0.87

A 0.47 0.47 0.47 0.96 0.96

B 0.48 0.56 0.48 1.63 0.96 C: control group; A: group A; B: group B

ex-ceed microbiological limit Jhaveri et al [54] reported that

an initial mesophilic aerobic count of iced Atlantic

day 15 Eifert et al [65] reported hybrid striped bass

Handumrongkul and Silva, [66] however, reported a count

of 6–7 log cfu/g for striped bass after 12 days of under MAP

refrigeration Reddy et al [6] found initial aerobic bacteria

counts and anaerobe bacteria count in MAP packed tilapia

were 4.3 and 3.2 log cfu/g, respectively This count reached

packed tilapia samples Villemure et al [4] reported

packed gutted cod are lower than in air packed samples

the amount of mesophilic bacteria count in herring flesh

at the time of rejection in MAP (10 days) and in vacuum

initial TVC of iced sardines 4log cfu/g, reaching the limit

packing and at day 10, for MAP Bacterial spoilage under

aerobic storage conditions of refrigerated fish to

Gram-negative psychrotrophic organisms dominated by

Pseu-domonas spp and Shewanella spp [67] Psudomonas are

effectively inhibited by atmospheres enriched with 20% or

more of carbon dioxide although Shewanella is more

inhib-ited by higher carbon dioxide concentrations (about 40%)

<3 log cfu/g for groups A and B samples, respectively,

during the 5 day period of storage refrigerator Many

bac-teria are endowed with histidine decarboxylase activity, but

only few species have been associated with histamine pro-duction during fish spoilage [49] Vaz-Pirez and Barbosa [69] reported for seafood the Enterobacteriaceae limit as

3 log cfu/g Statistical analysis showed significant

differ-ences only for the Enterobacteriaceae counts results in

Cor-relation between microbial counts and histamines results

determined for control group sardine: r, 0.6657; for group

A sardine: r, 0.8401, and for B group sardine: r, 0.9248.

Ruiz-Capillas et al [10] found initial of Enterobacteriaceae counts 2.92 log cfu/g in hake slices They also stated that

the Enterobacteriaceae counts increased to value of 4–5

log cfu/g in MAP samples in 10 days The inhibitory

storage in 14 days Initial Pseudomonas spp counts of all

samples after 7 days of storage whereas the MAP samples could not reach this content (3 log cfu/g) after 5 days of

reduc-ing anaerobe Clostridia’s counts ranged from 0.47–0.48 log MNP/g for control and MAP sardine samples These counts exceed very high levels after 5 days of storage in all group fish samples

Microbial counts (total plat count, psychrotrophic

Clostridias, Pseudomonas, Enterobacteriaceae), biochem-ical parameters (pH, total volatile nitrogen, trimethylamin

sardine (Sardina pilchardus) under MAP atmosphere

(%)) and air atmospheres were determined Control group samples (in air atmosphere packing) were unfit for human

5/35/60 (%)) were spoiled after 5 days Group B samples

3 days and ‘good quality’ up to 7 days The samples were

unfit for human consumption after 7 days

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