Method for preservation of fresh fish or sea-food

Abstract: A gas mixture comprising carbon dioxide, oxygen and argon is provided to extend the shelf life of sea-food products and fish from 15 to 21 days at the storage temperature of 4°C. Comparison is made with similar mixtures comprising nitrogen in lieu of argon which shows the unexpected results obtained with the mixtures of the invention.

Description: Background of the invention The usual industrial practice of catching fish or harvesting sea-food product is to bring them on board of the fishing boat where further process of the catch is operated or not. Most of the time, fishing boats are operating in campaigns along which they remain at sea for 5 days or more : therefore, it becomes necessary to process the catch as soon as possible and prevent it from turning bad. This is especially true for the catch of the early days of the campaign. A common practice is to store the catch in a refrigerated space mixed with an equivalent amount of crushed ice. When brought back to the port, the catch is either sold of fresh or more likely processed in various ways such as canning, smoking or freezing. As soon as the catch is taken out of its living environement (sea water), degradation processes start. Chemical and bacteriological reactions are the major sources of fresh fish and sea-food degradations. Bacterial contamination has many origins. Part of it comes from ambient air, but handling, cleaning and storing operations are the major responsible factors for contamination of the product. When living in its natural environment, edible parts of fish or sea-food have an extremely low level of contamination (inferior to 10 germs/g. However, it is not unusual to observe that level rising to 10⁴ or more germs/g after the product has been through every processing step. The highest the initial level of contamination, the fastest the deterioration of the product will be and ultimately, part of the caught stock has to be destroyed because of its total loss of market value. For a long period of time, it has been suggested to extend the shelf-life of fresh sea-food and fish by packaging these products under modified atmosphere in order to limit the microbial development on it. It has also been suggested to use enriched or even pure CO₂ atmospheres. It is known from USP 3 851 030, 3 930 040 and French Patent 81/20784 to use, binary or ternary mixture of N₂ and CO₂, O₂/CO₂ or O₂/N₂/CO₂ with partial pressures in the range of 50 % N₂ / 50 % CO₂ or 30 % N₂ / 70 % CO₂ or 20 % O₂ / 80 % CO₂. These compositions are appropriate and efficient for the extension of the shelf life of these products. CO₂ has an inhibiting effect on a wide number of microbial germs and a good solubility whithin fats and moist products. Therefore, it has become a basic requirement in gas packaging techniques to use it with a partial pressure as elevated as possible inside of the container. However, for moist products such as sea-food and fish, partial pressures of CO₂ above 70 % have the tendency to acidify the product. Some bleaching effect of the product due to elevated CO₂ partial pressures may as well be observed. On the other hand, it has been shown that CO₂ does not have an inhibition effect on the growth of strictly anaerobic germs such as Clostridium. Fresh fish or sea-food can however be naturally contaminated with spores of Clostridium botulinum. In strict anaerobic conditions, these spores are susceptible to germinate and produce a toxic protein which is excessively dangerous for mankind. Risk of development is particulary high when the storage temperature of the package exceeds 4°C. This temperature has always been a difficult parameter to control all along the distribution chain of the product and it is absolutely necessary to prevent the development of this germ in case of an accidental temperature rise. Introducing oxygen inside of the container or package is a recognized and accepted method to avoid Clostridium developments and therefore, O₂ partial pressure of at least 5% are usually recommanded for the final formulation of the gas mix. Nitrogen is eventually used as a complementary gas providing space filling or dilution capacities, it is not effective for controlling the microbial development. It is known from FR-A-2 351 008, a process to preserve red meat in a gas tight container wherein a ternary mixture of carbon dioxide (15 - 20% vol), oxygen (40 - 48% vol) and nitrogen (35 - 40% vol) is used. In this document, some improvements regarding meat preservation are disclosed. It is known from EP-A- 224 469 to preserve food with a gas atmosphere comprising between 1 to 15% oxygen, to 1 to 20% carbon dioxide and the complement being nitrogen, with a humidity between 70 to 98% and at a temperature between 0° C to 15° C. It is known from Food Technology, vol. 34, n° 6, June 1980, p. 102 and JP-A-80/02271 to seal food such as nuts or the like in a bag with an atmosphere of CO₂ and Argon to prevent spoilage by mold growth. Using the various gas combination available today for sea-food of fish packaging is extending its shelf-life from 2 days (air) to 8 days (gas). Exceptionally, products featuring a very low level of initial contamination and low fat content can have their shelf-life extended to 12 - 15 days. However, considering the lenght of the fishing campaign, the transportation time required for the distribution of the product and the storage time on distributor's shelves, a shelf-life of 15 days is a minimum requirement for an efficient marketing of any fresh sea-food or fish products. Summary of the invention According to the invention, it is provided a gas mixture comprising carbon dioxide having a partial pressure in the range of 50% to 68%, oxygen having a partial pressure in the range of 5% to 20% and argon having a partial pressure in the range of 27% to 45%. These gas mixtures extend the shelf-life of sea-food products and fish from 15 to 21 days at a storage temperature of about 4° C, for a bacteriological contamination of said products of fish which is not higher than 10⁴ germs/g of said sea-food product or fish. These gas mixtures slow down the enzymatic reactions and/or the microbiological development inside and/or at the surface of said fish and sea food products. Storage temperature by 4°C means preferably that this temperature is from 4°C + 1°C to 4°C - 3°C i,e., about between 5°C and 1°C. In case of salted products, this temperature may be less. According to a preferred embodiment of the invention, the partial pressure ranges are respectively between 50 % to 65 % for CO₂, between 10 % and 20 % for oxygen and between 30 % to 40 % for argon (at about the same temperature and bacteriological contamination). According to another preferred embodiment of the invention, it has been unexpectedly found that a gas mixture comprising about 30 % argon, 50 % CO₂ and 20 % O₂ (partial pressures) is able to extend the shelf life of said sea-food product or fish to a period longer that 21 days without reaching the tolerable level of contamination (10⁴ germs/g of said product or fish). Detailed description of the invention Other and further features of the invention will be clearly understood by referring to the following examples and tables which has been chosen for purpose of illustration, along in with the claims. Examples 1 to 3 Fish scallops and shrimps have been selected to perform the following comparative examples. They have been packaged in a gas impermeable container under about atmospheric pressure by compensated vacuum technique or gas flushing technique, said container being further heat-sealed to avoid substantially any contamination from the external atmosphere surrounding said container. Those packaged products have been stored at a temperature of 4°C under atmospheres respectively of air (example 1), 30 % N₂, 50 % CO₂ and 20 % O₂ (example 2), both according to prior art, and 30 % argon, 50 % CO₂ and 20 % O₂ (example 3), according to the invention. Results regarding the contamination type after 7, 14 and 21 days of storage are summarized in the following Table 1. From these results, it can be seen that after 21 days of storage, the 30% Ar/50 % CO₂/20 % O₂ product feature a total level of bacteriological contamination close to 10⁴ germs/g of product as compare to more than 10⁵ germs/g of product for the 30 %N₂/50 %CO₂/20 %O₂. Bearing in mind that 10⁵ germs/g is, in various countries, the tolerable limit for the bacteriological contamination level of a fresh product, it can be seen from these results that the gas mixture (30 % Ar, 50 % CO₂, 20 % O₂) is able to extend the shelf-life of sea-food to a period longer than 21 days without reaching the tolerable level of contamination. Examples 4 to 6 : The chemical and enzymatical degradation of the products stored (as explained before) under air and modified atmospheres were examined as well. The value of the amount of volatile nitrogen (Amino compounds produced from chemical and enzymatical degradation of proteins) was measured in every sample with the mean of the total volatile amino bases method (TVAB), for fresh scallops and shrimps. The results obtained are summarized in Table 2. From the above table 2, it is obviously shown that the gas mixture according to the invention is considerably slowing down the chemical and enzymatical degradations of fresh sea-food products. The use of a mixture according to the invention furthermore provides an inhibition effect on the growth rate of some microorganismes, such as fungis like Neurospora crassa as argon is known to have such an effect (see for example "General biological effects of the helium - Xenon series of elements" H.R. SCHREINER. Federation Proceedings - Vol 27 - N°3 - May - June 1968 - or "growth response of Neurospora crassa to increased partial pressures of the noble gas and nitrogen" - RG. Bachheit, H.R. Schreiner, G.F. Doebler - Journal of Bacteriologics, Feb 1966 - American society for Microbiology).

Claims: A method for fish and sea-food products preservation comprising the steps of placing said product in a gas impermeable container, pulling vacuum in said container introducing in said container a gas mixture comprising, in partial pressure, from 50% to 68% carbon dioxide, 5% to 20% oxygen and 27% to 45% argon, maintaining said introduction of gas mixture to reach a predetermined level of pressure inside said container, then sealing said container to avoid substantially any contamination from the external atmosphere surrounding said container A method according to claim 1, wherein said predetermined level of pressure is the ambient pressure. A method according to claim 1 or 2, wherein said products are packaged according to gas flushing/packaging method. A method according to one of claims 1 to 3, wherein said products are selected from the group consisting of fresh, processed, unprocessed, smoked and/or salted products. A method according to one of claims 1 to 4, wherein said container is an individual serving tray. A method according to one of claims 1 to 5, wherein said container is a bulk container. A method according to one of claims 1 to 6, wherein the storage temperature is comprised between 5° C and 1° C. Use of a gas mixture for fish and sea-food products preservation, said mixture comprising, in partial pressure, from 50% to 68% carbon dioxide, 5% to 20% oxygen and 27% to 45% argon, said mixture slowing down enzymatic reactions at the surface and inside said fish and sea-food products. Use of a gas mixture for fish and sea-food products preservation, said mixture comprising in partial pressure, from 50% to 68% carbon dioxide, 5% to 20% oxygen and 27% to 45% argon, said mixture slowing down the microbiological development at the surface and inside said fish and sea-food products. Use of a gas mixture according to claim 8 or 9, wherein said mixture comprises from 50% to 65% carbon dioxide, 10% to 20% oxygen and 30% to 40% argon. Use of a gas mixture according to claim 8 or 9, wherein said mixture comprises 50% CO₂, 20% O₂ and 30% argon.

Inventors: SAUNDERS RICHARD, SCHVESTER PASCAL, SAUNDERS, RICHARD, SCHVESTER, PASCAL
Applicants: AIR LIQUIDE, AIR LIQUIDE AMERICAN, L'AIR LIQUIDE, SOCIETE ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES  GEORGES CLAUDE, LIQUID AIR CORPORATION
Application year: 1989
Main classification: A23B4
IPC codes: A23L3, A23B4