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Maximising the Value of Marine By-Products

Maximising the Value of Marine By-Products

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Maximising the Value of Marine By-Products

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1,158 página
10 horas
Lançado em:
Nov 30, 2006
ISBN:
9781845692087
Formato:
Livro

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Despite declining stocks, a major portion of the harvest of fish and marine invertebrates is discarded or used for the production of low value fish meal and fish oil. Marine by-products, though, contain valuable protein and lipid fractions as well as vitamins, minerals and other bioactive compounds which are beneficial to human health. Devising strategies for the full utilization of the catch and processing of discards for production of novel products is therefore a matter of importance for both the fishing industry and food processors. Maximising the value of marine by-products provides a complete review of the characterisation, recovery, processing and applications of marine-by products.

Part one summarises the physical and chemical properties of marine proteins and lipids and assesses methods for their extraction and recovery. Part two examines the various applications of by-products in the food industry, including health-promoting ingredients such as marine oils and calcium, as well as enzymes, antioxidants, flavourings and pigments. The final part of the book discusses the utilization of marine by-products in diverse areas such as agriculture, medicine and energy production.

With its distinguished editor and international team of authors, Maximising the value of marine by-products is an invaluable reference for all those involved in the valorisation of seafood by-products.
  • Learn how to devise strategies for the full utilisation of the catch
  • Understand the importance of marine by-products to human health
  • Explores the use of marine by-products in diverse areas such as agriculture, medicine and energy production
Lançado em:
Nov 30, 2006
ISBN:
9781845692087
Formato:
Livro

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Maximising the Value of Marine By-Products - Elsevier Science

Shahidi

Maximizing the value of marine by-products: an overview

F. Shahidi,     Memorial University of Newfoundland, Canada

The world’s annual catch of fish and marine invertebrates has been around 100 million metric tonnes in recent years. However, aquaculture developments have led to production of high quality products that have also assisted conservation strategies to be implemented. Of the total amount of harvest, a major portion remains unused or used for production of fish meal and fish oil. This is due to the fact that certain species might suffer from small size, high bone, skin and fat contents as well as unappealing shape. In addition, several species of fish may be used for their roe and production of caviar. The leftover carcass following roe extraction as well as those of their male counterparts may be discarded. Furthermore, processing discards from many species of fish and shellfish could be successfully processed for production of specialty enzymes, xanthophylls, chitin/chitosan, glucosamine and other value-added products. Thus, devising of strategies for full utilization of the catch and processing of discards for production of novel products is warranted (Shahidi, 2000).

Seafood processing by-products and their use

The seafood processing industry is still producing a large quantity of byproducts and discards. These include heads, tails, viscera and backbone as well as shells. Utilization of these processing by-products may be exercised in different ways leading to

1. production of animal and aquaculture feed, similar to that used for whole fish when producing fish meal and fish oil,

2. production of food ingredients such as extraction of cheeks and tongue from cod and production of surimi from frames and

3. production of novel and value-added products for nutraceutical, pharmaceutical and fine chemical industries (Table I.1).

Table I.1

Physiological components from marine by-products

Novel and specialty products with potential biological activity and/or functionality provide a means for value-added utilization of by-products. These may be used as food ingredients to take advantage of a specific flavour, such as those from cook water of crab and lobster (Jayarajah and Lee, 1999; Yang and Lee, 2000), or for rendering a specific functional property such as water-holding, foaming, emulsifying and gelling properties. The use of by-products as health food ingredients may be for nutritional purposes; these include proteins, lipids, mineral and vitamins. Finally, by-products may be employed for nutraceutical and specialty applications. In this category, protein hydrolyzates, fish oils, hormones, glucosamine, chitin/chitosan, flavourants and enzymes as well as other physiologically active ingredients may be included. The following sections provide a cursory account of current and potential uses of by-products in different applications and for rendering health benefits.

Proteins from seafoods and their by-products

Seafood by-products are an excellent source of high quality proteins that may supply a major part of the essential amino acids that are required for a balanced nutrition. Recovery of proteins from by-products may be carried out by different processes using mechanical separation from frames, base extraction or hydrolysis. While hydrolysis of fish proteins by endogenous enzymes prior to or during primary processing may lead to fish quality deterioration, such processes may be intentionally carried out to produce specialty products. Thus, production of fish sauce and silage from fish and processing discards is commonplace. In addition, enzymes that are commercially available may be used to produce protein hydrolyzate that could be used in a variety of applications. Protein hydrolyzates are nearly colourless and appear like milk powder; they may be used in applications where water solubility and water-holding capacity are important. Protein hydrolyzates may possess biological activity in enhancing immune response and may also render antioxidant as well as angiotensin converting enzyme (ACE) inhibitory activity (Je et al., 2004) among others.

Carotenoids (C40H56) and their oxygenated derivatives (xanthophylls) are another group of bioactives that are present in salmonid fish, crustaceans and their processing by-products, among others (Shahidi et al., 1998). These are often present in combination with proteins, known as carotenoproteins. Extraction and isolation of carotenoproteins as ingredients for potential use in salmonid fish aquaculture has been reported (Cremades et al., 2003).

Digestive proteases from fish and shellfish processing discards may be used as industrial processing aids (Shahidi and Kamil, 2001). Suggested uses of digestive proteases from fish include acids for cheese making, herring fermentation, fish skinning, roe processing and production of specialty kits, as well as medical applications.

Lipids from processing by-products

Seafood lipids provide unique health benefits to consumers, but also present a challenge to scientists and technologists for delivering their highly unsaturated fatty acids (HUFA) in an odour-free and appealing form. The oils originate from the body of fatty fish as a by-product of fish meal industry, liver of white lean fish such as those of cod and halibut, and finally blubber of marine mammals such as seals and whales. Viscera from fish also provide for a rich source of lipids. These lipids include a high proportion of long-chain polyunsaturated fatty acids (LC PUFA) belonging to the omega-3 family, namely eicosapentaenoic acid (EPA), docosapentaenoic acid (DPA) and docosahexaenoic acid (DHA). There is a rapidly growing body of literature illustrating the health benefits of HUFA. These effects include protection against cardiovascular disease, autoimmune and mental disorders, diabetes, arthritis and arrhythmia, among others (Shahidi and Finley, 2001; Shahidi and Miraliakbari, 2004, 2005).

Marine lipids are highly prone to oxidation, hence their processing under relatively mild conditions and stabilization following refining, bleaching and deodorization is recommended. This is partly due to the fact that the refining process leads to the removal of endogenous antioxidants from the oil and hence replenishment with antioxidants, particularly those from natural sources is important. In addition, microencapsulation of the oils may prove useful when such oils are to be used in fortification of food and beverages.

Minerals and chitinous materials

Seafood processing discards contain a large proportion of frames as well as shells that are primarily composed of calcium salts. Thus, the resultant calcium may be solubilized and potentially used for addressing concerns about bone health due to insufficient intake of calcium. Jung and co-workers (2006) have clearly demonstrated the solubilization of calcium from fish frames and their benefits.

Most shellfish, especially those from shrimp, crab, lobster and crayfish contain a large amount of chitin that may be recovered following deproteinization and demineralization. The recovered chitin may be used for chitosan production using concentrated base or render pressure, glucosamine preparation or chitosan oligmers, short-chain copolymers of glucosamine and N-acetylglucosamine and derivatives thereof.

Glucosamine, the monomer of chitosan, has been reported to possess benefits for joint health and build up as well in wound-healing, among others. The product is generally sold as glucosamine sulphate, but this is often a mixture of glucosamine hydrochloride and sodium or potassium sulphate. Furthermore, glucosamine may be sold in combination with chondroitin 4- and 6-sulphates. Chondroitins are mucopolysaccharides (MPs) with molecular weights of up to 50,000 Da and could be prepared from connective tissues of slaughtered animals and seafoods (Jo et al., 2005). In combination, while glucosamine helps to form proteoglycans that sit within the space in the cartilage, chondroitin sulphate acts as a liquid magnet (Shahidi and Kim, 2002).

Future trends and prospects

Dwindling supply of seafoods from the wild dictates full utilization of the harvest. In addition, the advent of aquaculture allows a better control over the harvest time and hence better quality of products, including processing byproducts. A stricter environmental restriction on dumping of discards also serves as a further incentive to explore novel uses of products that might otherwise be considered uneconomical. Low temperature activity of enzymes as well as unique characteristics of products from processing discards might also catalyze new developments in value-added utilization of specialty products from processing lines.

References

Cremades, O., Parrado, J., Alvarez-Ossorio, M. C., Jover, M., Collantes-De-Teran, L., Gutierrez, J. F., Bautista, J. Isolation and characterization of carotenoproteins from crayfish (Procambarus clarkii). Food Chem.. 2003; 82:559–566.

Jayarajah, C. N., Lee, C. M. Ultrafiltration/reverse osmosis concentration of lobster extract. J. Food Sci.. 1999; 64:93–98.

Je, J. Y., Park, P. J., Kwen, J. Y., Kim, S. K. A novel angiotensin converting enzyme inhibitory peptide from Alaska pollack (Theragra chalcogramma) frame protein hydrolysate. J. Agric. Food Chem.. 2004; 52:7842–7845.

Jo, J. H., Do, J. R., Kim, Y. M., Kim, D. S., Lee, T. K., Kim, S. B., Cho, S. M., Kang, S. V., Park, D. C. Optimization of shark (squatina oculata) cartilage hydrolysis for the preparation of chondroitin sulfate. Food Sci. Biotechnol.. 2005; 14:651–655.

Jung, W. K., Lee, B. J., Kim, S. K. Fish-bone peptide increases calcium solubility and bioavailability in ovariectomised rats. British J. Nutr.. 2006; 95:124–128.

Shahidi, F.Seafood in Health and Nutrition - Transformation in Fisheries and Aquaculture: Global Perspectives. St. John’s, NL, Canada: ScienceTech Publishing Co, 2000.

Shahidi, F., Finley, J. W., Omega-3 Fatty Acids: Chemistry, Nutrition, and Health Effects. ACS Symposium Series 788. American Chemical Society, Washington, D.C, 2001:330.

Shahidi, F., Kamil, Y. V.A. J. Enzymes from fish and aquatic invertebrates and their application in the food industry. Trends Food Sci. Technol.. 2001; 12:435–464.

Shahidi, F., Kim, S.-K. Quality management of marine nutraceuticals. In: Ho C.-T., Zheng Q.T., eds. Quality Management of Nutraceuticals. DC: American Chemical Society. Washington; 2002:76–87. [ACS Symposium Series 803].

Shahidi, F., Miraliakbari, H. Omega-3 (n-3) fatty acids in health and disease: Part 1 - Cardiovascular diseases and cancer. J. Med. Food. 2004; 7:387–401.

Shahidi, F., Miraliakbari, H. Omega-3 fatty acids in health and disease: Part 2 - Health effects of omega-3 fatty acids in autoimmune diseases, mental health and gene expression. J. Med. Food. 2005; 8:133–150.

Shahidi, F., Metusalach, Brown, J. A. Carotenoid pigments in seafoods and aquaculture. Crit. Rev. Food Sci. Nutr.. 1998; 38:1–67.

Yang, Y., Lee, C. M. Enzyme-assisted bioproduction of lobster flavor from the process by-product and its chemical and sensory properties. In: Shahidi F., ed. Seafood in Health and Nutrition - Transformation in Fisheries and Aquaculture: Global Perspectives. St. John’s, NL, Canada: ScienceTech Publishing Co; 2000:169–194.

Part I

Marine by-products characterisation, recovery and processing

Outline

Chapter 1: Physical and chemical properties of protein seafood by-products

Chapter 2: Physical and chemical properties of lipid by-products from seafood waste

Chapter 3: On-board handling of marine by-products to prevent microbial spoilage, enzymatic reactions and lipid oxidation

Chapter 4: Recovery of by-products from seafood processing streams

Chapter 5: Increased processed flesh yield by recovery from marine by-products

Chapter 6: Enzymatic methods for marine by-products recovery

Chapter 7: Chemical processing methods for protein recovery from marine by-products and underutilized fish species

1

Physical and chemical properties of protein seafood by-products

T. Rustad,     Norwegian University of Science and Technology, Norway

Publisher Summary

It is a challenge to utilize more protein fractions from fish by-products as food ingredients. Many protein-rich marine by-products have a range of dynamic properties and can potentially be used in foods as binders, emulsifiers, and gelling agents. Fish proteins have unique functional properties such as capacity to bind water, lipids, rheological properties, etc. but, due to lack of a suitable purification process to preserve protein functionality, fish protein has been lacking in the rapidly growing protein ingredient and health markets. This chapter discusses the physical and chemical properties of protein seafood by-products. The functional properties of proteins are defined as physical and chemical properties that affect the behavior of proteins in food systems during processing, storage, preparation, and consumption. The sensory properties of foods result from interactions between several functional ingredients. The physical and chemical properties that determine protein functionality include the size and the shape of the proteins, the charge and the distribution of charge and the flexibility as well as the ratio between the hydrophobicity and the hydrophilicity. Handling, processing, and storage of raw materials will all affect the functional properties and it is therefore important to both characterize the functional properties of the raw material and find out how the different processing steps will affect these properties.

1.1 Introduction

Overexploitation of fish resources is a major problem as only 50–60% of the catch is used for human consumption. Globally, more than 91 million tonnes of fish and shellfish are caught each year. Some of the by-products are utilised but huge amounts are wasted. Annual discard from the world fisheries has been estimated to be 25% of the catch. Only a small amount of the by-products is used for human consumption, the rest is used for production of fishmeal, silage and animal feed. A list of valuable components in fish by-products is given in Table 1.1. Fish provides about 14% of the world’s need for animal proteins and 4–5% of the total protein requirement (Venugopal, 1995). The amino acid composition and digestibility of fish proteins is excellent. It is a challenge both to increase the utilisation of the protein fractions from marine by-products and to use more of these valuable proteins as food ingredients.

Table 1.1

Valuable components of fish by-products

Use of by-products is not new. In the Nordic countries a lot of the byproducts have been and are still being used for various purposes. For instance fish skin has earlier been used to cover window openings, to make clothes, shoes, carrier packs and sacks. Some fish by-products that are used for human consumption include roe (canned, salted/marinated or as cod roe emulsion), liver (Eastern Europe), cleaned stomach, fried fish milt (a snack) and head products from Iceland (cheeks, tongues, dried heads).

In 2000 a total of 251 000 metric tonnes of by-products were created by the Norwegian cod fisheries alone, of this 114000 tonnes were dumped while 137 000 tonnes were utilised. Only 33 000 tonnes of the by-products were used for human consumption which amounts to about 13% of the total (RUBIN, 2001). The rest is used for production of fishmeal, silage and animal feed. A large part of the by-products that are dumped at sea are made up by heads (Stoknes and Hellevik, 2000). In Norway only about 20% of the cod heads are exploited. Of this 9000 tonnes goes to human consumption, mostly as dried heads to Nigeria. In some fisheries the tongues and cheeks are cut out. The rest is minced and used as feed for fur animals.

Fisheries and fish industries are the single most important industry in Iceland. In 2001 the total catch was around 2 million tonnes, accounting for 62% of the value of exported products and around 48% of the foreign currency earnings that year. Fish meal and oil constitute the bulk of the volume of products from fisheries in Iceland or 63% of total, but their value is far less or only about 14% of the total value of exported seafood products. In 2001, Iceland exported about 45 500 tonnes of by-products with a value of US$73.5 million.

Of a total available UK fish and shellfish resource of approximately 850000 tonnes, only 43% end up as products for human consumption. The rest is categorised as ‘waste’. About 300 000 tonnes of this is produced on shore, whereas the rest is produced at sea (145 000 tonnes discarded fish and 43 000 tonnes processing waste). For cod-fish these numbers can be broken down to 154 000 tonnes on shore and 37 000 tonnes at sea. In the UK the major outlet for this raw material is fishmeal and oil production, only small quantities are used for other purposes (pet food, animal feed, fishing bait, etc.). In some areas of the UK the by-products primarily end up in landfill sites. Much of the waste production is concentrated in regional processing centres. Only very few fishing vessels utilise the by-products. The non-utilised by-products generated onboard are dumped at sea.

The annual harvest of seafood in Alaska is over 2 million tonnes and yields more than 1 million tonnes of by-products, some of this is produced into fishmeal and oil but the majority is discarded (Crapo and Bechtel, 2003; Sathivel et al., 2004).

1.2 Overview

The protein-rich by-product fractions include cut-offs, backbones, heads, skin, roe, milt, stomachs, viscera and blood. The proportion of different by-products from different species is given in Table 1.2. For the industry to be able to utilise more of the by-products, data on the available amounts as well as on the chemical composition and the properties of both the protein and the lipid fractions as a function of species, season and fishing ground are needed.

Table 1.2

Amount of different by-product fractions

Includes bellyflap

On average, production of cod fillets will generate two-thirds of the whole body weight as by-products. The data of Falch et al. (2006a) show that the viscera (all inner fractions) makes up 12–15% of the whole body weight of four Gadidae species (cod, saithe, haddock and tusk), caught in the Barents sea, the head 15–20% and the backbone and trimmings (cut-offs) make up 18–30%. In a study including 750 specimens from five different Gadidae species caught at three different fishing grounds in Europe, the viscera was found to constitute 3–7% of the round weight of the fish. The highest proportion was found in the Norwegian Gadidaes and the lowest in the Irish (Falch et al., 2006b).

For Gadidae species caught in Icelandic water, the proportion of intestines in tusk and ling was lower than in the other cod species (Thorarinsdottir et al., 2004). The proportion of liver, roe and milt were positively correlated, but negatively correlated to viscera and CF (condition factor). The proportion of head was similar for all cod groups (different sizes of cod), ranging from 27 to 33%. The proportion of head of tusk, ling, saithe and haddock was lower than that of cod. The proportion of backbone varied from 14.9 to 16.3% for cod and from 14.9 to 18.7% for haddock. The size of the cod did not affect the proportion of the backbone. The proportion of skin from cod fillets was in the range 5.1 to 7.7%. It was highest for ling (8.7 to 10.8%) and tusk (10.6 to 12.4%) at all seasons. Cut-offs in cod groups were in the range 9.5 to 12.0%, in haddock in the range of 7.7 to 11.7%, in saithe 10.5 to 15.6%, ling 12 to 15.4% and in tusk 11.5 to 13%. Seasonal effects were not significant.

The global production of farmed Atlantic salmon was estimated to be 1025 000 tonnes in 2002 (Globefish, 2002) and more than 50% of this weight is regarded as by-products or waste. The largest fractions constitute the cut-offs (including backbone) (14%), viscera (13%) and head (10%), and these fractions might serve as a source of valuable marine lipids and proteins. Blood makes up 2% of the total weight of salmon.

The composition of different by-product fractions from different species is given in Table 1.3. In different sources reporting protein content in various byproduct fractions, the protein content is usually given as crude protein, Nx6.25, this value also includes the NPN (non-protein-nitrogen). In some fractions this may constitute up to 25% of total N (Sikorski, 1994). In the meat of white fish, the NPN content is usually from 9 to 15% of total N. About 95% of NPN is made up of free amino acids, dipeptides, trimethylamine oxide (TMAO) and degradation products, urea, guanidine, nucleotides and degradation products of nucleotides.

Table 1.3

Protein content in different by-product fractions

Includes bellyflap

Liaset et al. (2000, 2002) reported that the protein content of cod frames was 16.9% while the content in salmon frames was 17.4%. In another study, the protein content in salmon frames was found to be 18.2% (Michelsen et al., 2004) and the protein content in salmon viscera was found to be 10.6%.

Sikorski et al. (1984) have reported protein content in different fish skins to be between 18 and 35%, with a collagen content between 10.6 and 28.8%. Sikorski (1994) reported the crude protein content in different fractions of fish from New Zealand waters. The protein content in viscera varied from 7.5 to 23.9% while the content in skin varied between 11.9 and 29.6% and in frames the protein content was between 13.1 and 25.3%.

Fish roe has high concentrations of proteins and lipids (Bledsoe et al., 2003). In general fish roe products are high in protein (16–30%). Crude lipid content can vary from less than 5% to 20% with an average of 10% in salmon roe. The protein quality of fish roe is high, either methionine/cystine or tryptophan/tyrosine are the limiting amino acids.

The backbone is one of the major by-product fractions, yielding about 15% of the fish weight (Gildberg et al., 2002). About 15% of the wet weight is pure bone, the rest is white muscle (Jeon et al., 2000). The bone makes up about one-third of the dry weight and consists of minerals (60–70%) and proteins (30%). The protein is mainly collagen (Lall, 1995; Nagai and Suzuki, 2000). Based on these values, it can be calculated that 80–85% of the protein in cod backbone fraction is muscle protein and the rest is collagen. Gildberg et al. (2002) found that the muscle proteins from the backbone fraction could be extracted using hydrolysis with commercial enzymes and the resulting bone could be used to recover gelatine using heat extraction. The gelatine extracted had a low molecular weight, but could be suitable for technical applications and nutraceuticals.

Flesh from backbones and cut-offs may be a suitable raw material for production of fish mince, surimi and surimi-based products. Surimi is mechanically deboned fish flesh that has been washed with water or dilute salt solutions and to which cryoprotectants have been added. Surimi is used as the raw material for preparation of seafood analogues, such as shrimp, crab legs, scallop and lobster tail. In addition the surimi industry has the potential to develop new products. Øines et al. (1995) found that the yield of fish mince that could be separated from salmon and white fish cut-offs and backbones was between 48 and 56% of the weight of the by-product fractions with a protein content ranging from 13 to 17%.

The demand for collagen and gelatine from the industry throughout the world is considerable and still rising. By-products from fish processing are a potential source of collagen. In fish the largest collagen concentrations are found in the skeleton, fins and the skin (Norland, 1989; Sikorski and Borderias, 1994). Fish gelatine and collagen have been much less studied than mammalian gelatine and collagen (Norland, 1989; Gudmunsson and Hafsteinson, 1997). Mammalian collagen in its purified form has found a number of pharmaceutical and cosmetic applications. Similarly, gelatin, the hydrolysed form of collagen, is an ingredient extensively used in the food industry. Gelatin is used as a food additive to improve the texture, the water-holding capacity and stability of several food products (Borderias et al., 1994). Some documents also suggest that fish collagens were used in ancient times. Plinius (AD 23–79) speaks of ‘ichtyocolla’ (fish glue) from Pondus (The Black Sea), and Plinius the Elder reports use of fish glue as a medicine against headaches and cramps (Solstad and Muniz, 2001).

The quality and specific application of the extracted collagen and gelatine is highly related to their functional properties and to purity. Known problems with the extraction of collagen from fish skins are the abundance of pigments and the presence of fish odours, which would restrict its potential use. The uniqueness of fish collagen from cold water fish lies in the lower content of amino acids, proline and hydroxyproline (Haard et al., 1994). Although fish gelatine does not form particularly strong gels, it is well suited for certain industrial applications, as, for example, micro-encapsulations, light-sensitive coatings, and low-set-time glues. The extraction of native collagen, as described by van de Vis et al. (1996), instead of gelatine, which is the hydrolysed form of collagen, is strongly preferred, because native collagen provides more and better opportunities to modify the functional properties as well as the possible applications of collagen in the food ingredient industry.

The skeleton, fins and skin constitute the main part of whitefish ‘offal’. The Norwegian fish industry produces approximately 600 000 metric tonnes of ‘waste’ per year. This includes 10000–12 000 tonnes of skins from white fish (cod, pollack, haddock, etc.) which could be used to produce at least 1500–2000 tonnes of fish gelatine (RUBIN, 2001). The search for new gelling agents to replace mammalian gelatine has led to patents for fish gelatine production (Grossman and Bergman, 1992; Holzer, 1996) as well as several published methods (Gudmunsson and Hafsteinsson, 1997; Nagai and Suzuki, 2000; Gomez-Guillen and Montero, 2001). Collagen from fish has just recently been identified as a potential allergen and this may be a potential problem for the use of fish gelatine in commercial products (Sakaguchi et al., 1999; Hamada et al., 2001).

Fish milt is a product that is often wasted, even though canned milt from cod and herring is a traditional food product in England (Gildberg, 1999). The milt contains a high amount of protamine and nucleic acids and is used for industrial production of nucleic acids. The products are used in health food and cosmetics and the remainder used as feed supplement in aquaculture. Studies have shown that supplementation of cod milt cationic proteins to the feed of juvenile fish may improve their resistance to V. anguillarum infection (Pedersen et al., 2004).

Real caviar is made from sturgeon, but a wide variety of other fish roes are consumed in their own right, as well as products sold as substitutes for sturgeon roe. Important commercial fish roes include salmon roe (Ikura), lumpfish roe, flying fish roe, whitefish roe, cod roe, mullet roe, herring roe (Kazunoko), pollack roe (Bledsoe et al., 2003).

A wide variety of by-products have been used for making fish silage (Gildberg, 2002). Fish silage can be produced from all kinds of low-value fish and fish by-products and is almost entirely used for feed. Fish silage is normally made by mixing 2–3% formic acid into the minced raw material and storing at ambient temperatures till endogenous enzymes have dissolved the fish tissue. A well-preserved fish silage will normally have a pH of 3–4 which is the optimum pH for fish pepsins. The process usually takes a few days, provided that the raw material has a sufficiently high content of pepsins and other acid proteases (cathepsins). The silage may be used directly in feed or processed further by separation of the oil and evaporation to give a protein concentrate. The advantage of producing fish silage is the low capital investment and simple processing equipment. The disadvantage is the high transport costs due to the high water content. Norway is the major fish silage producer – producing about 140 000 tonnes per year, mainly from aquaculture by-products (salmon). Fish silage is a low price product, but is a good alternative for utilising by-products that might otherwise have been wasted.

A large proportion of the catch (~ 30%) is used for fish meal and animal feed because of its poor functional properties. One of the approaches for effective protein recovery from by-products is enzymatic hydrolysis, which can be applied to improve and upgrade the functional and nutritional properties of proteins (Gildberg, 1993; Liaset et al., 2000). Proteolytic modification of food proteins to improve palatability and storage stability of available protein resources is an ancient technology (Adler-Nissen, 1986). Hydrolysates can be defined as proteins that are chemically or enzymatically broken down to peptides of varying sizes. Today much of the fish flavour, fish soup and fish paste products available on the market are prepared by enzymatic hydrolysis (Shoji, 1990). Protein hydrolysates can be used as emulsifying agents in a number of applications such as salads dressing, spreads, and emulsified meat and fish products like sausages or luncheon meat (Badal and Kiyoshi, 2001). They can also be used in bacterial growth media (Poeronomo and Buckle, 2002).

A large variety of different fish protein hydrolysates are being produced. The oldest is fish sauce which has long traditions in South-East Asia. Fish sauce, which is the major fermented fish product, was known in Ancient Greece and Rome (Corcoran, 1963). Fish sauce is produced in a quantity of about 250 000 tonnes per year. It is made by mixing three parts of fish raw material with one part of salt and storing at ambient tropical temperatures for 6–12 months. Both endogenous and microbial enzymes contribute to the degradation of the proteins in the fish and the resulting fish sauce is an amber liquid with 8–14% digested proteins and about 25% salt. The production is simple and requires little sophisticated equipment, but there is a need for a large storage space (Gildberg, 2002).

Fish protein hydrolysates can be made with enzymes, acids or alkali. Enzymatic hydrolysis is strongly preferred over strictly chemical methods for producing hydrolysates for use in nutritional applications. Enzymatic hydrolysis can produce hydrolysates with well defined peptide profiles (Lahl and Braun, 1994). This approach gives an effective recovery of proteins, in addition to upgrading the functional and nutritional properties of the by-product proteins (Shahidi et al., 1995; Liaset et al., 2000; Slizyte et al., 2005). Enzymatic hydrolysis of fish by-products may be accomplished by an autolytic process, using the digestive enzymes of the fish itself or using added commercial enzymes, or by a combination of these (semiautolytic). The autolytic process lasts from a few days to several months. There are no enzyme costs involved and it is a simple operation. However, prolonged digestion may adversely affect the functional properties of the resulting hydrolysate, and such products are generally used in feed formulations. Semiautolytic processes including the endogenous enzymes as well as commercial enzymes may be the most interesting, but require knowledge about the raw material composition and the activity, stability and specificity of the endogenous proteolytic enzymes regarding variations according to species, season and fishing ground (Slizyte et al., 2005; Dauksas et al., 2004).

The development of fish protein concentrates (FPC) was one of the earliest attempts to recover fish protein from processing wastes. FPC has been produced using solvent extraction, resulting in a concentration of the proteins by removal of the water and oil from the raw material (Kristinsson and Rasco, 2000).

By-products from cod species are a potential source for bioactive compounds. This may be both secondary metabolites as well as enzymes, lipids and heteropolysaccharides (Gudbjarnason, 1999). Protamine is a basic peptide containing more than 80% arginine. Protamine has been found in the testicles of more than 50 fish species. Protamine has the ability to prevent growth of Bacillus spores and may be used as an antibacterial agent in food processing and preservation.

It has been reported that many proteins possess antioxidative activities, and fish protein hydrolysates have been found to be antioxidative (Amarowicz and Shahidi, 1997; Kim et al., 2001).

Proteolytic enzymes from cold-adapted fish have received a lot of interest in recent decades. These enzymes have been found to be more catalytically active at relatively low temperatures compared to corresponding enzymes from mammals, thermophilic organisms and plant sources (De Vecchi and Coppes, 1996; Gudbjarnason, 1999). Enzymes with unique properties for industrial utilisation can be recovered from fish by-products (Haard et al., 1994). The Icelandic Fisheries laboratory has developed a process to recover trypsin-like enzymes from cod viscera (Stefansson and Steingrimsdottir, 1990). In Norway industrial processes for recovery of pepsin, trypsin, chymotrypsin, alkaline phosphatase and hyaluronidase from fish viscera have also been developed (Almås, 1990). Alkaline phosphatase is recovered from the thaw water from frozen shrimp (Olsen et al., 1990). This is used in diagnostic kits.

1.3 Physical and chemical properties of protein-rich by-products – seasonal, habitat, species and individual variations

It is a challenge to utilise more of the protein fractions from fish by-products as food ingredients. Many protein-rich marine by-products have a range of dynamic properties and can potentially be used in foods as binders, emulsifiers and gelling agents (Sathivel et al., 2004). Fish proteins have unique functional properties such as capacity to bind water, lipids, rheological properties, etc. but, due to lack of a suitable purification process to preserve protein functionality, fish protein has been lacking in the rapidly growing protein ingredient and health markets. Retaining the functional properties through preservation and processing operations is therefore of great importance. The functional properties of proteins are defined as ‘those physical and chemical properties which affect the behaviour of proteins in food systems during processing, storage, preparation and consumption’ (Kinsella, 1976). The sensory properties of foods result from interactions between several functional ingredients. The physical and chemical properties that determine protein functionality include the size and the shape of the proteins, the charge and the distribution of charge and the flexibility as well as the ratio between the hydrophobicity and the hydrophilicity. Handling, processing and storage of the raw materials will all affect the functional properties and it is therefore important to both characterise the functional properties of the raw material and find out how the different processing steps will affect these properties.

Fish is regarded as an excellent source of high-quality protein, particularly the essential amino acids lysine and methionine. Comparison of PER (protein efficiency ratio) from cod muscle and cod by-products shows that fish byproducts have a high content of essential amino acids and can be used to produce products with high nutritional value (Shahidi, 1994). Hydrolysates also have a high chemical score and the amino acid composition is generally similar to that of the raw material, except for content of sulphur amino acids, histidine and tryptophan which are affected during hydrolysis (Quaglia and Orban, 1987; Shahidi et al., 1995; Kim et al., 1997). The content and properties of the proteins in marine by-products vary with regard to species, fishing ground and season. In order to increase the utilisation of the protein fractions, knowledge about these variations is necessary.

Seasonal differences in the amount of different by-product fractions were found, with a higher proportion of viscera during autumn and spring (Falch et al., 2006b). The Gadidae species caught in these waters spawn in the first six months of the year (January to June) and the proportion of gonads will therefore be highest during these months. The proportions of roe were, as expected, significantly higher in the autumn and spring. Higher proportions of roe were generally found in Gadidaes from Iceland and Ireland compared to Gadidaes from Norway. During the spawning season, the roe made up 2.2% of the round weight of fish on average. The lowest ratio of skin was found in spring and the highest in autumn for cod species from Icelandic waters (Thorarinsdottir et al., 2004).

Also the chemical composition of the by-products varies according to species, season, fishing grounds and growth conditions. The protein content in by-product fractions from five cod species collected at three different fishing grounds and three different seasons was analysed. Total protein content was highest in the cut-off fraction and lowest in the viscera. All fractions showed variation in protein content with fishing ground, species and season. Amount of water-soluble protein was highest in liver and cut-offs and lowest in the viscera; the low content in viscera is due to the high degree of degradation in this fraction. The amount of free amino acids was generally lowest in the liver and highest in the viscera. The degree of hydrolysis was lowest in the cut-offs and highest in the viscera. In some liver samples a high degree of hydrolysis was also found (Sovik, 2005). For cut-offs an inverse relationship was found between water and protein content (Thorarinsdottir et al., 2004); a similar relationship existed for roe.

In carp by-products seasonal differences in both the amount and properties of the proteins were found for both wild and farmed carp. The amount and properties of the proteins also varied between wild and farmed carp by-products (Bukovskaya, unpublished results). The protein content in cut-offs and gonads were higher in the wild than in the cultured carp. During summer, the content of water-soluble proteins did not differ significantly between cultured and wild carp. In winter a substantial increase of water-soluble proteins content in intestine of wild carp was observed. Liver had the highest content of free amino acids followed by viscera and cut-offs, a substantially higher content of free amino acids was found in the liver and viscera of cultured carp compared to wild carp. This reflects the influence of the feeding on the composition not only in the fish fillets but also in the by-products.

For products such as fish mince and surimi, the water-holding capacity and the gelling properties which determine the textural attributes of the products are important quality parameters (Venugopal and Shahidi, 1995). Knowledge of how to retain these properties during storage and processing is therefore important. Seasonal variations in water-holding capacity in cut-offs from cod species was noted, with a lower water-holding capacity found in autumn, except for small cod, tusk and haddock. Minced meat is less stable than intact muscle. By-products from filleting have the same good quality as the main products (fillets), but unfortunately are not always treated in the same way, resulting in a rapid loss in quality. If the by-products are intended for use in food, the frames and cut-offs should be stored at 0oC (Øines et al., 1995). Freezing of the raw material will generally lead to loss of both water-holding capacity and gel forming ability, but freezing of the cut-offs/frames may result in smaller reduction in these parameters than freezing of mince. Both the freezing temperature and time as well as thawing conditions may influence the loss of functional properties.

Gildberg (1993) found that the sauce fraction develops much faster if fresh intestines are used than if the material has been freeze-stored. The reason for this is not clear, but it is well known that freeze-storage of fish material implies a tougher tissue structure that may be less susceptible to digestion by enzymes. Another possible explanation is that bursting of lipid cells during freezing and thawing involves formation of a stable lipid-protein, emulsion which hinders a fast phase separation.

The quality of by-products limits the possibilities for utilisation of the raw material, and enzymatic activities along with microbial degradation are the most important factors determining raw material quality. Variations in enzymatic activities and therefore quality are important when finding possible uses for the different by-product fractions. In processes utilising by-products, such as production of fish protein hydrolysates (FPH), minced and surimi-based products, extraction of lipids, enzymes and/or other bioactive compounds, the activity of the endogenous enzymes in the raw material needs to be controlled and knowledge about how these activities change according to temperature is important.

Significant variations in quality parameters and enzymatic activities in byproducts from cod according to species, seasons and fishing grounds have been demonstrated (Søvik and Rustad, 2004, 2005a, 2005b). The highest overall proteolytic activity in the by-product fractions was found in viscera at pH 3 (35°C). Cut off and liver fractions also showed maximum activity at pH 3, 35°C and 50°C, respectively. Maximum median proteolytic activity in viscera is approximately 20 times higher than that in liver and 250 times higher than that in cut-off. Species affected the general proteolytic activity (pH 5 and 7), and activity of trypsin and chymotrypsin in viscera from cod species. Trypsin and chymotrypsin are the major proteolytic enzymes active at neutral pH in the viscera of cod species. Viscera from Atlantic cod, saithe and haddock had a higher proteolytic activity compared to tusk and ling. In cut-off and liver, general proteolytic activity (pH 5 and 7), activity of cathepsin B and collagenase varied according to species. Variations according to season were found in the activity of trypsin, chymotrypsin, elastase, cathepsin B, collagenase and lipase (pH 7) in the viscera from Atlantic cod. The results clearly indicated that viscera samples from the Icelandic sea had lower enzymatic activities in April–June compared to the other seasons. Cut-off samples from Icelandic Sea also had lower cathepsin B and collagenase activity in April-June compared to February-March; fishing ground influenced general proteolytic activity as well as activity of trypsin, chymotrypsin, elastase, cathepsin B, collagenase and lipase. Heat stability of the enzymes is also important and it has been shown that trypsin, chymotrypsin and cathepsin B in crude extracts from viscera from cod species lost 50% of initial activity after incubation for 10 min at 60°C, while elastase, collagenase and lipase lost 50% of their initial activity after incubation for 10 min at 50°C. The ratio between proteolytic activities in different by-products are similar in carp and cod and can be described as: INTESTINE > LIVER > CUT-OFFS (Søvik et al., 2004). In carp the difference in the levels of proteolytic activity in intestine, liver and cut-offs are less significant than in cod. Both in carp and cod, the total proteolytic activity in the intestine was highest at pH3 followed by pH 7 and lowest at pH 5. For cut-offs this correlation was similar between species: pH3 > pH5 > pH7 (Søvik et al., 2004).

The presence of proteolytic enzymes in the viscera of fish had a significant influence on the production of hydrolysates (Shahidi et al., 1995; Slizyte et al., 2005, 2006). When producing hydrolysates from capelin, endogenous enzymes alone gave a protein recovery of approximately 23% after 4 h at pH 3.0 (Shahidi et al., 1995). The hydrolysis of ground capelin by endogenous enzymes enhanced the overall extraction of fish protein at both acid and alkaline pH, since both acid and alkaline proteases are present in fish muscles and viscera. Pre-digestion of fish mince prior to the addition of exogenous enzymes might enhance the yield of protein extraction, however, autolytic enzymes may also bring about undesirable changes in the products, as it may be difficult to control the degree of hydrolysis during storage and processing. Furthermore, autolytic protease activity varies from species to species and depends on the season of harvest. Therefore, properties of functional protein hydrolysates may vary greatly under the same processing conditions. The chain length of the peptides formed during the hydrolysis process is important: this is one of the parameters determining both the functional and the organoleptic properties of the hydrolysate (Slizyte et al., 2005, 2006; Dauksas et al., 2004).

The high collagen content in skeleton, fins and skin which constitute the main part of whitefish ‘offal’ can become a problem when collagen turns into sticky fish glue in the production of fishmeal (Sikorski et al., 1984). In the production of fishmeal and oil from fish ‘offal’ problems can arise due to gelatinisation of collagen into fish glue causing problems in concentration of stick water and drying of fishmeal. The content of collagen is thought to contribute significantly to the viscosity of the stickwater.

Common problems connected with fish gelatin from cold water species are low gelling and melting temperatures and low gel modulus. The differences in physical and rheological properties between mammalian gelatine and gelatine from cold water species are due to a lower content of the amino acids proline and hydroxyproline (Sikorski et al., 1984). The quality and specific application of the extracted collagen and or gelatine is highly related to their functional properties and purity. There is also a market for non-gelling gelatine, which has a potential in the cosmetic industry as an active ingredient (i.e., shampoo with protein). Using fish collagen and gelatine generates new applications as a food ingredient, because it has properties different from mammalian collagen and because it can be used in food where mammalian gelatine from a cultural or safety point of view is not wanted.

Generally, the enzymatic activities in by-products are high and it is therefore important that they are rapidly and continuously stored at cold temperatures. It is also important that the by-products are treated as valuable raw material in the same way as the main product, starting from the time the fish is caught. Separating the different by-product fractions, and fractions from the Lotidae family from the Gadidae family, will ensure that fractions with low enzymatic activity are not contaminated by fractions with higher enzymatic activities. Viscera from Atlantic cod caught in the Icelandic sea and from fish from the Gadidae family may be better raw materials for protein hydrolysates, especially if autolytic or semi autolytic processes are used or for extraction of proteolytic enzymes. Viscera samples from Atlantic cod caught in the Barents Sea have lower lipase activity and may therefore be a better raw material for extraction of marine oils compared to samples from the Icelandic Sea. Cut-off from ling and saithe, Atlantic cod caught in the Barents Sea (April–June and October-December) and Icelandic Sea (April-June) may be used for minced products or surimi-based products. Cut-off from haddock, Atlantic cod caught at the south coast of Ireland and in the Icelandic Sea (February–March) is a poor raw material for these kinds of products due to the high activity of cathepsin B (Søvik, 2005). Results from this latter study also suggest that viscera should be kept separately. Contamination of liver and cut-off fractions with viscera fractions should be avoided.

1.4 Implications for by-products valorisation

To be able to produce value-added products from fish by-products for human consumption, it is necessary that the by-products are treated as a valuable raw material and the name should perhaps be ‘upgraded’ to rest of raw material. Efficient on-board handling and sorting of specific by-products are important to reduce the rate of enzymatic degradation and microbial spoilage. The enzymatic activities in by-product fractions are high and it is important that they are rapidly and continuously stored at low temperatures. Rapid sorting and separation of different by-product fractions so that fractions with high enzymatic activity do not contaminate the fractions of low activity is also important.

It is also possible to take the fish onshore ungutted and gut the fish in efficient processing lines onshore. In a Norwegian study, it was found that cod could be landed ungutted and gutted within 12 hours after catch without any negative effects on the quality of the fish or the by-products. Spawning cod with a low degree of filling in the stomach/intestines could be kept ungutted for up to 48 hours. Heavily feeding cod should not be stored ungutted for more than 12 hours. The quality of by-products (liver, gonads and stomach/intestine) from fish landed ungutted was found to be better compared to controls gutted immediately after catch and stored in bags on ice for up to 48 hours after catch (Akse et al., 2002).

There is a need to develop methods to preserve different by-product fractions. Methods of preservation and utilisation depend upon the application of the byproduct. It is important to specify the shelf life at different levels of processing and product quality changes during storage. Potential preservation methods may include chilling, freezing, drying, fermentation and use of preservatives such as natural antioxidants. These methods should be tested for bulk- and final products and the different fractions (fat, protein/gelatine) from the most valuable byproducts. The final products should be evaluated for their usage in food applications.

More research is also needed to develop processing methods to extract the fractions/biomolecules of interest. The processes developed should be able to handle variations on the basis of season, habitat and species. The processing steps should be optimised both regarding yield and product quality, but also about processing costs. Products should have as high quality as possible at the lowest possible price.

In order to evaluate possible applications for products and conservation techniques of the rest of raw material, it is important that the raw material is characterised based on its chemical composition and enzymatic activity. Characterisation of variation in chemical compositions has mainly been carried out on fish muscle. Limited work has also been done on the chemical characterisation of some fishery by-products. To obtain a total picture of the applications and potential for new use, detailed characterisation including seasonal, species and habitat variations is still needed.

For achieving profitable utilisation of by-products from the fish industry the final products require market interest. Knowledge about quality and composition is a necessity. The products and the processes to produce these must be economically viable. There is still great potential in utilisation of these fractions and a need for further investigations. There is also a need for environmental restrictions and economic incentives to increase the utilisation of marine byproducts.

1.5 Future

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