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Monday 20 May 2013

Types of Spoilage in Fish


Types of Spoilage in Fish

Fish is a highly perishable commodity. The Spoilage of fish being as soon as fish dies. In tropical conditions, fish spoils quite rapidly, within a few hours of landing, if not properly cooled. The spoilage rate of fish may be reduced by good handling practices and effective temperature control from very beginning.
            In raw fish, spoilage takes place mainly due to three reason viz.,
1)      Enzymic action
2)      Microbial action
3)      Chemical action
Enzymes and bacteria do not cause any deteriorative changes in the living cell because of the natural defensive mechanism. In dead fish, enzyme become involved in the autolytic changes and bacteria can invade the fish muscle and proliferate there. The fish gut is rich in proteolytic enzymes and in dead fish it digests the gut and belly region making the fish very soft. Bacteria that are present on the surface, gills and gut of the fish invade the dead fish, decompose the tissue and bring about undesirable changes. Off odor and off flavor, slime, gas production, discoloration and soft texture are the obvious signs of spoilage. Component involved in spoilage process are protein, lipids, carbohydrates, nucleotides and other non-protein nitrogen compounds. The rate of spoilage is temperature dependent and lowering the temperature will reduce the rate of spoilage.
A)     Autolytic spoilage (Enzymatic):-
            Autolytic spoilage is responsible for early loss of quality of fresh fish. The first enzymatic change in fish muscle is the gradual hydrolysis of glycogen to lactic acid which is known as glycolysis.

1)      Glycolysis:-
            After death, the blood circulation stops and the cells longer supplied with oxygen and hence glycogen will not converted into the carbon dioxide and water unlike in the case of living cells. In the postmortem period, glycolysis proceeds via the anaerobic pathway where the end product is lactic acid. As the lactic acid accumulates, the pH of the muscle falls. In fish, glycolysis will continue until the supply of glycogen is completely used up. In general, fish muscle contain relatively low amount of glycogen compared with mammalian muscle and the final postmortem pH is consequently higher. This makes the fish meat more susceptible to microbial attack. 

2)      Flavor changes in fish ( Nucleotide degradation):-
The most significant enzyme deterioration is those that alter flavor. The nucleotide degradation in fish muscle produces many flavor bearing compounds. These compounds are formed by the splitting of ATP by series of dephosphorylation and deamination reaction.
ATP              ADP              AMP           IMP                Inosine                Ribose                Hypoxanthine
Progressively it is hydrolyzed to ADP (Adenosine diphosphate), AMP (Adenosine monophosphate) and to IMP (Inosine monophosphate) and ammonia. At ambient temperature, ATP breakdown occurs rapidly and IMP accumulates in the fish tissue. In fresh fish, the rate of IMP is very high and it imparts a desirable sweet, meaty and characteristic flavor to fish. As autolysis proceeds further, the level of IMP decreases and neutral tasting Inosine or bitter tasting hypoxanthine accumulates in tissue. As a result, fish becomes more insipid. Some of these compounds increases with time and have been used as indices of fish freshness.
3)      Belly bursting:-
Enzymic spoilage causes belly bursting in fish, especially during a period of high food intake. These fishes will have a large content of digestive enzymes in the digestive tract. Such fish will degrade quickly and spoil easily soon after they are caught. In the dissolve gut components, bacteria proliferate and produce gases such as CO2, and H2. This gas production leads to belly bursting after short storage period. Keeping the fish live for some time will retards this.
4)      Color changes in the fish:-
Color is an important factor in seafood quality. Color change in seafood is caused by Enzymic or non-enzymic action such as fat oxidation or by pigments. Color change in the seafood is an indication of spoilage. The important discoloration in seafood caused by enzymes or fat oxidation is illustrated below:
a.      Black /blue discoloration
i)                    Shrimp:-
            The development of black spot in shrimp is due to the presence of an enzyme, polyphenol oxidase (PPO). The black spot (melanin) is formed by the oxidative reaction of tyrosinase on tyrosine. Different species of shrimp undergoes postmortem discoloration to different extents. The pigment is formed on the internal shell surfaces, or in advanced stages, on the underlying shrimp meat. This makes the shrimp unattractive for marketing. The shrimp phenol oxidase differs from that found in mussel or lobster in that it is not activated by trypsin. Sulphite preservatives can be used to prevent black discoloration resulting from phenolase reaction. Dipping shrimp in 0.2 – 0.5 % sodium bisulphite for one minute is usually adopted in industrial practice.

ii)                  Lobster:-
Black spot occurrence during icing and frozen storage of lobster is serious problem which has resulted in significant commercial losses. Tyrosinase activity was identified in the blood with lesser amounts in other tissue. Discoloration at the butt of the tail, black spot between the segments and other deteriorations are more pronounced in moribund lobster. The tendency for blackening is also influenced by moulting cycle.
iii)                Crab:-
Phenolase has been implicated in blue – black coloration of crab. The enzyme is present in the blood. Various additives have been shown to prevent blue discoloration (e.g. organic acid, sodium bisulphite and EDTA). The haemocyanin induced blacking is also prominent in crab and is non-enzymic.
b)  Yellowing of fish flesh:-
Frozen storage of some fish may result in yellowing of flesh below the skin. Freezing or other processes disrupt chromatophores and release Carotenoids and their migrations to the subcutaneous fat layer causes yellowing. Yellowing associated with lipid oxidation and carbonyl –amine reaction is observed during frozen storage.
c)  Brown discoloration:-
Brown or yellow discoloration is caused by the reaction of the protein or the amino acids with product of lipid oxidation. Brown discoloration is observed in verity of processed products including white pomfret, sardine, jack mackerel, salted shark, marine eel, etc. Discoloration due to protein – lipid browning is greater in fatty fish than lean fish.
B)     Microbial spoilage:-
Fish spoilage is mainly due the action of bacteria. Bacteria are present on the surface slime, skin, gills and intestine of fish. In dead fish bacteria begin to invade the tissues causing spoilage and production of undesirable compound. The type of bacteria on the fish is very much depending on the microbial flora of the environment. However, in the fish processing industries two types of micro-organism are of concern.  
1)      Saprophytic or spoilage type bacteria:-
These organisms are responsible for the spoilage of the fish. The important classes of spoilage organisms found in tropical species are Pseudomonas, Flavobacteria, Acinetobacter, Aeromonas and Moroxella. The spoilage bacteria are characterized by their ability to produce H2S, reduce Trimethlyamine oxide (TMAO) to Trimethlyamine (TMA) and convert urea to ammonia. Many volatile sulphur compounds are also produced by Pseudomonas.
A quantitative measurement of these compounds indicates the degree of spoilage. Fish flesh starts visibly to spoil when bacterial level rises to above 107 organisms per gram.
The flesh losses its culinary qualities like juiciness, firm texture, etc. changing it into a product that becomes soft with loss of flavor, discoloration and off flavor. The major deteriorative changes brought about by microorganisms in fish are the following.
a)      Formation of ammonia:-
Spoilage organisms convert many nitrogen compounds into off smelling volatile bases. Non-protein compound present in fish are good substrate for spoilage organisms. The free amino acid pool in the muscle of fish is readily utilized by typical spoilage organism by the process of deamination. This result in the formation ammonia which is the primary compound produced during decomposition of fresh fish. Ammonia is the major component in the total volatile nitrogen (TVN) fraction which often is used as a quality indicator for fresh fish. Area present in elasmobranches like shark and rays is degraded to ammonia by bacterial action. Thus, high level of ammonia in these species is an indication of spoilage.
b)     Formation of TMA:-
Marine fish is characterized by the presence of an odorless compound called Trimethlyamine oxide (TMAO). Marine flat fish and teleost contain low level of this compound (0.1-0.5%) while elasmobranches (shark, rays, etc.) and gadoids contain very high level (1 to 1.5%). Spoilage bacteria convert this substance into foul smelling Trimethlyamine (TMA). TMA is produced in fish muscle slowly at first then at greater speed in fish stored at ambient temperature, in ice or in refrigerated seawater. The fishy odor is produced when it reacts with fat.    
c)      Histamine formation:-
Microbial spoilage of fish produces the toxin, histamine in certain fishes. Histamine poisoning or scombroid fish poisoning is very frequent in many countries. Scombroid fishes and other dark muscle fishes contain high level of free amino acid, histidine in their muscle. During spoilage histidine is converted into histamine by bacteria. Over fifty species including popular species such as Tuna, Bonito, Mackerel, Blue fish, Dolphin fish (Mahi mahi), sardine, carangids, herring, and anchovies were shown to be potential threat of histamine poisoning. Histamine production increases with temperature and 370 C is the optimum temperature for the microbial activity. Morganella morganii, Hafnia alvei, etc. are the main spoilage organisms producing histamine. Low temperature storage, right from catch, reduces histamine production.
d)     Indole production:-
Conversion of tryptophan to indole is another result of amino acid decomposition by bacteria. The FDA uses indole level along with sensory evaluation for measurement of shrimp decomposition.
e)      Other compounds formed during bacterial spoilage:-
A number of extractives are available in fish for bacterial action such as free amino acids, sugars, peptides, creatine, as well as lipid and proteins. Chemical examination of spoiling fish muscle as shown that organoleptically the most important constituents are the volatile sulphur compounds such as hydrogen sulphide (H2S), dimethyl sulphide(CH3)2S and methylmercaptan (CH3SH). Ester of lower fatty acid such as acetic, Propionic, butyric, hexaenoic acid etc. are also produced. Volatile sulphur compounds influence the organoleptic characters, especially odors; in spoiling fish. The overall qualitative chemical picture of spoiling fish in summarized below:
Substrate
Compounds produced by bacterial action
Inosine
Hypoxanthine
Carbohydrate and lactate
Acetic acid, CO2  & H20
Methionine & Cysteine
H2S, CH3SH and (CH3)2S
Tryptophan
Indole
Glycine, Leucine & Serine
Esters of acetic, Propionic, butyric and hexaenoic acids
Trimethlyamine oxide
Trimethlyamine
Urea
Ammonia
Lipids
Carbonyls
Proteins
Tyrosine, Indole, skatole, putrescine, cadaverine
Histidine
Histamine

Some of the spoilage bacteria proteolytic and undoubtedly contribute to the ammoniacal odor by producing ammonia from the protein breakdown.
2)               Pathogenic bacteria:-
The pathogenic bacteria associated with seafood’s are of two types:
a)      Indigenous bacteria:-
They are widely distributed in the aquatic environment. These pathogens occur in minimal numbers and are not a serious problem in fresh fish. However, their growth and multiplication in seafood is a serious problem and can cause illness.
Eg. Clostridium botolinum, Vibrio sp., Aeromonas sp.

b)     Non-indigenous bacteria:-
They occur in seafood as a result of contamination. The source include polluted aquatic environment, sewage, excreta from animals, birds, human being, workers handling the material as well as the surface and environment where the seafood is processed.
Example Salmonella sp, Shigella sp., E. coli, and Staphylococcus aureus
C)     Chemical spoilage (oxidation of the fish lipids):-
Fish lipid is characterized by a high level of polyunsaturated fatty acids (PUFA) and hence undergoes oxidative changes. With fatty fish in particular, fat oxidation give rise to problem such as rancid flavour and odor as well as discoloration. Lipid oxidation is by two process (a) Auto oxidation – action of O2 on the unsaturated fatty acids and (b) Lipid hydrolysis – an enzymatic hydrolysis with free fatty acids (FFA). Oxidative rancidity is of great concern in the fatty fish storage. In pelagic species like sardine, mackerel and herring, rancidity has been detected during spoilage. At first hydro peroxide are formed, which further degrade to form aldehyde and ketones with typical rancid flavor. The oxidation is initiated and accelerated by heat, light (UV radiation), presence of several organic or inorganic compounds (e.g. Cu and Fe), moisture content, large surface area, presence of air etc. Antioxidant such as tocopherols, ascorbic acid, citric acid or Carotenoids can inhibit oxidation.
Factors affecting spoilage:-
The rate at which spoilage occur varies with species of fish, sanitary conditions, methods of handling and storage. The rate of spoilage is highly temperature dependent. Increase the temperature from 0 to 50 C doubles the spoilage rate of many species of fish. So, chilling the fish immediately after catch (rapid chilling), careful handling, gutting and maintaining good hygiene will retard the spoilage rate.

General Aspect of Sea Food Quality
Definition of Quality:-
Quality is generally considered as degree of excellence. It also related to the price of the commodity, its composition nutritive value, degree of freshness, hazards to health and satisfaction on eating.
            Quality Assurance:-
At the implementation level of quality assurance may be divided into two parts, firstly “Quality Assurance” and secondly “Quality Control”.
            Quality Assurance: - This includes the following points.
1)      Establish good manufacturing practices suitable for unit.
2)      Establish product specifications.
3)      Design quality control programme.
4)      Identify critical control points for inspections.
5)      Establish laboratory procedure.
6)      Ensure regulatory compliance and safety in the plant.
7)      Divide programmes and procedures to improve yield.
8)      Develop effective market and product recall system.
Quality control:-
Quality control in case of seafood is necessary steps, taken to protect the quality of final product.
Uniqueness of seafood quality control
Quality control of seafood differ that of any other food. Agricultural product can be harvested under ideal condition that is right time food is harvested at right time and right place. This meant that it is possible even to select the right species to rare them at desire level of growth and harvest them in a predetermine place as per predetermine scheduled. In the case of seafood harvesting is from sea, rivers and other water areas from the stocks of unknown identity. Hence the intrinsic quality varies in all possible variations. Another phenomenon which complicates quality of seafood is unpredictability of catch. At time catches may exceed the handling capacity. Sometimes catches are very poor and processing unit may remain idol together. Another problem of tropical fishery is presence of large number of spp.

Quality control setup
Depending on size of production unit quality control is the responsibility of single individual or department. The quality control unit should include representative from all important section from seafood processing unit.
e.g. Pre-processing , production, machine room, quality control room, packing.
Responsibilities of quality control department
1. Formulation of specification of raw materials, plant process, container and finish products.
2. Development of test procedure and testing of quality of products.
3. Development of sampling schedule.
4. Preparation of form for recording and reporting.
5. Attending to any problem during production and suggesting suitable solution.
6. Maintenance of personal hygiene and sanitation.
7. Assuring the increase customer satisfaction.
8. Training of personal of labor.
9. On line inspection with special reference to CCP.
10. Inspection and proper storage packaging material.
11. Inspection and proper storage of ingredients, cleaning agents and sanitizers.
12. Maintenance of production and processing equipments also ensuring the proper maintenance of cold storage.
13. Maintenance of the laboratory and analysis of the same.
14. Checking the records of the machine including log book of cold storage and freezers. 
 
Quality problem in sea food industry-     
Sea food product can be broadly divided in to two groups,
1.      Export products
2.      Domestic product
The quality of product in both cases has to be good. Some of the most common quality problems usually encountered in these products are described below,

1.      Poor quality raw material- one can notice wild variations in quality of raw material received in sea food plant.
2.      This problem is dependent on size of the fishing craft, facility for icing and storage of fish onboard of fishing vessel. Facilities for further preservation and storage at landing center. Sanitary condition onboard vessel, preprocessing and processing vessel.
3.      Following pre-cautions need to be taken to maintain the quality of raw material.

a.      Sand adhering to fish or shrimp is washed off before starting any processing.
b.      Dressing should be carried out properly.
c.       Broken pieces should be kept separately in case of shrimp.
d.      The raw material temperature should be never being allowed to exceed 20C.
e.      Good quality ice and water should be used in processing.
f.        Strict hygienic and sanitation condition should be maintained in processing.
               Black spot in shell on shrimp-
A black spot formation in shrimp processing industry is enzymatic reaction and requires access to oxygen addition to the presence of heavy metal like cupper and iron. The pigments are produced by an oxidative reaction on tyrosine (amino acid). By this discolourizition eating quality is not loosed but it mass appearance which affect the marketing of shrimp. Melanosis can be prevented by cutting down oxygen contact, lowering temperature or by using sodium metabisulphide or potassium metabisulphide.  
Inspection certification:-
Three systems of inspection & certification have been recognized under the fish & fishery products. They are,
1.      Quality Control & Inspection in Approved Units: -
 QCIA unit should have the prescribed programme supports and processing control. They also keep the necessary records. The final product is subjected to regulatory agency such as EIA, to check whether they meet to the all standards as prescribed or lay down. Standards are issued with certificate for export.  Regular monitoring of the unit is also done to ensure the prescribed sanitary standards are maintained or not and hygiene requirement are of complete satisfactory levels.


1.     In Process Quality Control: -








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