Fish Oils: Production and Properties

AK Carvajal and R Mozuraityte, SINTEF Fisheries and Aquaculture, Trondheim, Norway

ã 2016 Elsevier Ltd. All rights reserved.

Introduction human consumption, the freshness criteria are based on the

total volatile basic nitrogen (TVB-N), which shall not exceed
The total world fisheries and aquaculture production was 158 60 mg of nitrogen/100 g.
million tons in 2012, of which 136.2 tons were used for Storage and transport must be carried out under hygienic
human consumption and 21.7 million tons of the catch and conditions by using tanks of stainless and mild steel construc-
aquaculture production was used for fish oil and fish meal tion. The catch has to be chilled within 24 h. Fishing of pelagic
production. The global fish oil production is estimated to be species used for fish oil and meal production is mainly done by
about 1 million tons per year (0.980 tons in 2012 according to purse seiners and the fish is stored in bulk in refrigerated sea
FAO). Out of the estimated 1 million tons of fish oil, about water (RSW) tanks at
1.5  C on-board. Whole fish being
70 000 tons is estimated to be used for human consumption. processed within 36 h must have an acceptable freshness cri-
Peru and Chile are the largest producers of fish oil (around teria based on TVB-N. Rest raw material may be used directly
295 000 tons in 2012), followed by Norway and Denmark after production at the slaughter lines to produce oil or may be
(140 000 tons in 2012) and Iceland (around 176 tons in chilled and transported in containers to the production site.
2012). Norway is the largest global importer of fish oil Organic acids can be added to the rest raw material to conserve
(approximately 200 000 tons) followed by Chile, United the raw material before further processing (production of
Kingdom, and Canada. silage). However, the use of non-food-grade acids will result
in fish oils that can be used in feed and not for human
consumption.
Marine Sources for Fish Oil Production

Marine sources used for fish oil and fish meal production can
Fish Oil Production
be divided into four categories:

(1) Fish caught especially for the production of oil and meal. Fish oil and fish meal are traditionally produced by the wet
This includes species such as anchovy, jack mackerel, cap- rendering method. The first step is mincing of the raw material
elin, menhaden, and blue whiting. By-catches from other (whole fish or by-products), followed by cooking. The cooked
fisheries can also be included in this category. material is separated into different fractions, resulting in pro-
(2) By-products/rest raw material from the processing industry duction of crude fish oil and fish meal. A simplified scheme of
(both fisheries and aquaculture). the oil and meal production is given in Figure 1.
(3) Cod liver (from Gadus morhua L. or other gadidae species).
(4) Other marine resources such as seal, krill, micro algae, etc.
Cooking
Raw Material Quality
Minced whole fish or by-products are transferred to a contin-
uous cooker and steam heated to 90–95  C for approximately
The quality of the fish oil depends on the sorting, storage, and
10–20 min. The heating will cause protein coagulation and
handling of the raw material. Fish rest raw material is especially
rupture of fat depots, resulting in liberation of oil and water.
vulnerable to spoilage and degradation because it contains
The cooker usually consists of a long, steam-jacket cylinder
fractions like viscera and blood with high amounts of endog-
where the raw material is moved by a heated rotary screw
enous enzymes. Lipases and phospholipases will lead to for-
conveyer. The procedure normally takes around 20 min; how-
mation of free fatty acids (FFAs) and reduction in quality and
ever, if a scraped surface heat exchanger is used, the heating
stability of the lipids. Prolonged storage of the rest raw material
time can be reduced to less than 2 min.
before processing has been shown to lead to an increased
concentration of FFA, thus lowering the quality of oil produced
from herring and pollock rest raw material. Proteolytic
enzymes will cause a reduction in the molecular weight of Pressing
protein, thus reducing the functional properties. Rest raw
materials are also susceptible to microbial spoilage and it is After cooking, the heated material is transferred to a screw press
important that they are handled as a raw material intended for where the liquid (‘press liquor’) is squeezed from the solid
human consumption. To ensure high quality oil, it is impor- phase (‘press cake’) in order to remove as much liquid as
tant to process the raw material within a short time. possible. Optimal pressing will lead to a higher oil yield and
There are some regulations for the raw material for fish oil if a lower amount of oil in the press cake; thus, a fish meal with
it is going to be used for human consumption or feed. If the low oil content. The press cake liquid consists of water, dis-
whole fish is going to be used for fish oil production for solved material, and oil, while the press cake consists of

Encyclopedia of Food and Health http://dx.doi.org/10.1016/B978-0-12-384947-2.00294-4 693

694 Fish Oils: Production and Properties

Whole fish or
cut-offs from fish

Cooking

Pressing Press cake Dryer Cooler

Press Liquor Grinder

Solids Removal Solids

Fish meal
Oil-water Seperation Stick water Evaporator

Crude fish oil

Figure 1 Simplified scheme of oil and meal production.

60–80% of the oil free dry matter. The press cake is further pro-oxidants in the oil, thus increasing the oil stability during
processed into fish meal. storage. After polishing, the oil is pumped into storage tanks.
The produced oil is called crude fish oil.

Separation of Press Liquid

Drying of Press Cake
Before the oil and water is separated, the press liquid is passed
over a vibrating screen (with 5–6 mm perforation) to remove Sludge separated from the press liquor is mixed with the press
unwanted coarse particles of fish and bones. Different proces- cake together with the concentrated stick water. The press cake
sing solutions based on the fractions’ different specific gravity is then dried to reduce the moisture content to a level low
can be used for separation of the press liquid (oil, water, and enough to hinder microbial growth. Two types of driers are
remaining solids). First, a decanter (horizontal centrifuge) can used in the fish meal industry: direct and indirect driers. In
be used to remove fine suspended solids from the liquor in direct driers, the press cake is in direct contact with the hot
order to obtain an oil and water phase suitable for further gases, while in indirect driers the heat is transferred to the cake
separation. The oil and water phase is transferred to a centri- through a retaining wall. Indirect driers are mainly used in the
fuge for separation into oil and stick water (water soluble fish oil industry.
components). The oil is pumped to a polishing centrifuge
while the stick water is transferred to the evaporator.
An alternative separation technique is to use a tri-canter Enzymatic Protein Hydrolysis
which enables the separation of three fractions (sludge, oil, and
stick water) at the same time. However, industry experience New processes for production of oil based on enzymatic
indicates that it is difficult to produce three high quality fractions protein hydrolysis are being developed and applied in the
and in many cases one of the fractions has to be downgraded in industry. Enzymatic protein hydrolysis is based on the use
order to produce the other high quality fractions. of commercial proteases for proteolytical cleavage of peptide
bonds, facilitating the degradation of fish tissue and release of
oil. The advantages of using enzymatic hydrolysis compared
Oil Polishing to the wet rendering method could be a protein product with
better biological, digestible, and functional properties. In
A polishing centrifuge can be used to remove the final traces of addition, the use of lower cooking temperature (50–60  C)
moisture and impurities in the oil. This reduces the amount of compared to the wet rendering method (90–95  C) can
 Fish Oils: Production and Properties 695

give an oil of higher quality (low oxidation status) and • Short path distillation (SPD): further reduction of POPs,
stability. removal of cholestereol, primary and secondary oxidation
For processing of whole fish and by-products by enzy- products, FFAs, and polymeric materials
matic hydrolysis, a hydrolysis stage has to be implemented
Which refining steps are included and in which order can vary
after the material is minced. The reaction can take place in
between the different fish oils processors.
either a tank reactor or a screw-mixing pipe reactor. Heated
minced raw material is transferred to a hydrolysis tank and
mixed with water (usually in a 1:1 ratio) and commercial
proteolytical enzymes (0.1–1 wt% of raw material weight). Neutralization
The reaction proceeds for 30–90 min (hydrolysis time),
followed by enzyme inactivation at 90  C for several Neutralization is carried out to remove FFAs (lowering the oils’
minutes. acid value) and reduce the content of phospholipids,
Several factors can influence the hydrolysis process: sub- pigments, and trace metals. FFAs can cause darkening of the
strate type and properties, enzyme type and properties, and oil, foaming, and possible smoke during heating. During
processing conditions including temperature, pH, hydrolysis neutralization, the oil is mixed with caustic soda, resulting in
time, and amount of added water. These factors are important the formation of soaps that can be separated from the crude
for product yield and quality and need to be controlled during oil. The oil is heated to the optimum processing temperature of
processing. 80–95  C before caustic soda is added. Hot water is then added
to the solution, mixed, and the soapy wash water is removed by
using a separator. Washing with water will also remove any
water-soluble components present in the oil such as decompo-
Krill Oil Production sition products of proteins, free amino acids, trimethyl amines
and histidine, oxidation products, and phospholipids.
The krill oil industry has developed and optimized the produc-
tion process for krill, resulting in different processing steps and
end products (oil, meal, pasta, etc.). Processing details are Winterization
often confidential and little is published in the literature. The
most common process is to pump live krill onboard the factory Winterization is carried out to reduce the amount of high
trawler were the krill is frozen or directly processed into krill melting point triacylglycerols and waxes in the crude oil. The
meal. The dried meal can be transported to shore and used to process is carried out in tanks with inert conditions and the oil
extract krill oil by solvent extraction. is slowly chilled to 0–2  C allowing the formation of triacyl-
glycerol crystals with higher melting points to settle and be
removed by filtration. The winterization process prevents
clouding of the oil at refrigeration temperatures.
Production of Refined Fish Oil

Crude fish oils contain minor amounts of water and unwanted

Bleaching
substances as phospholipids, mono- and diacylglycerols,
FFAs, cholestereol, proteinaceous compounds, trace metals,
The bleaching step removes pigments, but will also further
pigments, and primary and secondary oxidation products.
reduce the content of FFAs, residual trace metals, and oxidation
The crude oil needs to go through different refining steps
products (peroxides) that are left in oil after neutralization. In
before it can be used for human consumption. The general
addition, the process will also remove soaps and sulfur-
objective of refining of oils is the removal of impurities and
containing materials. Bleaching by using activated carbon
unwanted products which cause the crude oil to have an unat-
reduces the residual traces of environmental pollutants such
tractive color or taste or can cause harmful metabolic effects.
as dioxins, furans, and PAHs. However, the process will also
The refining process can include the following steps:
reduce the content of desirable natural antioxidants present in
• Neutralization by addition of citric acid or caustic soda: the oil as retinol, tocopherol, cholecalciferol, and astaxanthin.
removal of mainly FFAs, but also oxidation products, phos- The process is carried out by adding bleaching earth and/or
pholipids, pigments, trace metals, and residual soaps activated carbon to the oil through a dosing unit. It is per-
• Washing with hot water: removal of water-soluble material, formed at 130–150  C for 30–60 min under vacuum.
oxidation products, trace metals, and soaps
• Winterization
• Bleaching by using bleaching earth and activated carbon: Deodorization
removal of pigments, peroxides, phospholipids, soaps,
trace metals, sulfur compounds, persistent organic pollut- The deodorization step is carried out to remove as much as
ants (POPs), polycyclic aromatic hydrocarbons (PAHs), possible of the unwanted volatile compounds (secondary oxi-
retinol, tocopherol, and astaxanthin dation products such as aldehydes, ketones, etc.) that are
• Deodorization (steam stripping): removal of volatile com- responsible for the unwanted odor and taste of the oil. How-
pounds, aldehydes, ketones, POPs, FFAs and pigment ever, possible nonvolatile secondary and tertiary oxidation
decomposition products products that are formed during processing will not be removed
696 Fish Oils: Production and Properties

by deodorization. The oil is steamed under vacuum at a high oleic acid, 20:1 n
9 gondoic, 22:1 n
11 – cetoleic, 20:5
temperature (150–250  C) to remove the volatiles. The process n
3 – eicosapentaenoic and 22:6 n
3 – docosahexaenoic
is also called stripping, desorption, or steam distillation when fatty acids. The triacylglycerols consist of fatty acids esterified
oil is mixed with stripping gas to facilitate the mass transfer of at three different positions on a glycerol molecule. This distri-
the volatiles to the gas phase. The gas phase is continuously bution of fatty acids in the glycerol molecule is more or less
removed from the liquid phase. Deodorization should be car- unique for different types of natural fat. An indication of
ried out at a maximum temperature of 180  C to reduce the risk approximate composition of various fish oils are given in
for polymerization and geometrical isomerization. Table 1. In most of the fish oils the omega-3 LC PUFAs, mostly
EPA and DHA, generally make up 10–35% of the total fatty
acids. Fatty acids such as 20:1 and 22:1 are present in signifi-
Molecular (Short Path) Distillation cant parts in oils produced from fish such as herring, mackerel,
and capelin, caught in northern waters.
An additional step can be added to the refining line to reduce
trace amounts of POPs such as dioxins, PCBs, and furans. The
use of short path distillation will also lead to the reduction of Other Chemical Constituent
odor compounds, FFAs, oxidation products, and polymers
formed during decompostion/oxidation of the oil. Short path Fish body and liver oils contain other chemical components
distillation is also used in the production of omega-3-acid such as vitamins. Vitamin D tends to concentrate in the liver of
ethyl esters. fish. Therefore, body oils contain less vitamin D compared to
liver oils. The content of vitamin D depends on the species, age,
size, sex, nutritional conditions, and spawning state of the fish.
Fish Oil Properties The liver oils also contain vitamin A. Vitamin E is not synthe-
sized by fish; therefore, vitamin E content is dependent on the
Physical Properties
fish diet. The most abundant form of vitamin E is alpha
Many of the physical properties of fish oil are dependent on the tocopherol with the concentration being higher in the liver
composition of fatty acids and on the nature of their incorpo- than body oils. The level of tocopherol in fish oil is reduced
ration into acylglycerols. Density is one of the characteristic during refining and deodorization and generally less than
that determines quality of the oil and is usually in the range 100 ppm is found.
920–930 kg m
3. Density increases as the mean molecular
weight decreases (i.e., with higher saponification values) and
the degree of unsaturation increases. Fish oil is a liquid above Oxidative Stability
10  C and can solidify below this temperature. The viscosity of
fish oils at 20  C ranges between 60 and 90 cP and decreases Because fish oils usually contain long chain polyunsaturated
exponentially with increasing temperature, the regression fatty acids, they are highly susceptible to oxidation. In addition
equation being 121e
0.028T where T is in the range of to fatty acid composition, the oxidative stability of oils also
20–90  C. depends on the amount of prooxidants and antioxidants in the
Fish color can vary depending on the species of fish used oils and storage conditions such as temperature, light, and
and processing conditions. oxygen availability. Anoxic production and storage of oils pre-
vent against oxidation. Generally, each 10  C decrease in stor-
ing temperature doubles the shelf-life of the oil. Trace amounts
Chemical Properties
of prooxidants (catalysts of lipid oxidation) such as transition
Fish oil is usually made up of triacylglycerols, which often metals are usually present in fish oils. Therefore, in order to
account for more than 95% of the lipids in the oil. The char- reduce oxidation, antioxidants that inactivate metals or lipid
acteristic of a specific triacylglycerol is dependent on the fatty radicals are added to the fish oils. Encapsulation of n-3 fatty
acids composition. However, some fish oils, for example, shark acids reduces the contact between lipids and oxygen and
oil, can comprise 40–50% ether linked glycerides. Some fish contributes to protection against oxidation. Packaging in mate-
species can have wax-esters as dominant storage lipids. Wax rial nonpermeable for light and oxygen also contributes to
ester–rich oils generally contain lower levels of omega-3 LC protection against oxidation.
PUFA. Lipid oxidation is a dynamic process creating a complex
mixture of primary, secondary, and tertiary products. Because
several products are intermediate; they are formed and then
Fatty Acid Composition broken down again during marine oil processing, and there is
not always a linear increase in the oxidation-products with
The fatty acid composition of fish oils is complex and variable. time of oxidation.
The composition of fish oils in terms of fatty acids is usually The oxidative state of oil is defined as the sum of all oxida-
determined by chromatographic methods. The fatty acids tend tion products present. Traditionally, an estimate of primary
to contain an even number of carbon atoms and double bonds (peroxide value) and secondary products (anisidine value) is
are of the ‘cis’ configuration. applied.
The most abundant fatty acids in fish oils are: 14:0 – PV analysis usually is performed using the iodometric titra-
myristic; 16:0 – palmitic; 16:1 n
7 – palmitoleic; 18:1 – tion method—that is, the one referred to both by Ph. Eur.
 Fish Oils: Production and Properties 697

Table 1 Composition of major fatty acids of selected fish

Fatty Percentage composition

acid
Farmed Atlantic Jack Atlantic cod Atlantic South American Sardine/
salmona Tunaa mackerela liverb menhadenb anchovyb pilchardc Capelinc Herringc

14:0 4.2 3.9 7.3 3.3 7.3 7.5 8 7 7

16:0 15.7 17.6 15.7 13.4 19 17.5 18 10 16
18:0 4.2 4.1 3.1 2.7 4.2 4 nd nd nd
16:1 5.1 5.4 5.1 9.6 9.1 9 10 10 6
n
7
18:1 16.5 12.4 9.9 23.4 13.2 11.6 11 14 13
n
9
18:1 3.5 2.4 2.9 nd nd nd nd nd nd
n
7
20:1 3.3 1.3 8.3 7.8 2 1.6 4 17 12
n
9
22:1 2.5 0.5 5.8 5.3 0.6 1.2 3 14 20
18:2 6.6 1.9 1.7 1.4 1.3 1.2 nd nd nd
n
6
20:5 7.1 12.4 10.9 11.5 11 17 18 8 5
n
3
22:6 15.7 27.8 11.5 12.6 9.1 8.8 9 6 6
n
3
22:5 3.9 1.7 2 1.6 1.9 1.6 nd nd nd
n
3
a
Nichols (2007).
b
Ackman (2006).
c
Bimbo (1990).

(Monograph 2.5.5 Method A) and by GOED (AOCS procedure Table 2 Chemical properties of crude oils
Cd 8–53).
Anisidine value (AV) determines the amount of aldehydes Quality guidelines for crude oils
(secondary oxidation products) formed as a result of break-
Moisture and impurities (%) Usual basis 0.5 up to maximum of 1
down of lipid peroxides in the oils. The method is based on the Fatty acids (% oleic acids) Range 1–7, usually 2–5%
color reaction between the aldehydic compound and the Peroxide value (mequiv. kg
1) 3–20
p-anisidine (AOCS procedure Cd 7–58, Ph.Eur. Monograph Anisidine value 4–60
2.5.36). TOTOX (2PV þ AV) 10–60
Oxidative stability of oils is usually difficult to determine. The Iodine value 95–200 (depending on fish source)
effect of different antioxidants on the oxidative stability of fish Color (Gardner scale) Up to 14
oils can be determined by accelerated oxidative stability methods Iron (ppm) 0.5–7.0
such as the oxidative stability index (OSI). The OSI method is an Copper (ppm) Less than 0.7
Phosphorus (ppm) 5–100
American Oil Chemist Society (AOCS) approved method that
determines the relative resistance of fat and oil samples to oxi-
dation. The instrument measures the conductivity increase in
deionized water as a result of the secondary products’ formation
during the oxidation of the oil. The Schaal oven test is another material. This will influence the properties of the oils in regard
accelerated method for determining the stability of lipids and the to edible properties and technical applications. No standard
effect of antioxidants. The test is based on the measurement of quality criteria are set for the crude oils, but an overview of the
weight gain of lipid samples over time at a chosen temperature. typical chemical and physical properties of the crude oils has
The increase in the weight is a result of oxygen binding to the been reported by Bimbo in ‘Guidelines for Characterizing
unsaturated fatty acids (i.e., peroxidation). Active antioxidants Food-grade Fish Oil’ shown in Table 2. Several tests are used
will delay the onset of peroxidation and, therefore, the weight to evaluate the quality, moisture content, and impurities. The
gain, compared to a control (no antioxidants). quality criteria for crude oils are mainly set by the buyer of the
oils depending on their range of application; feed, nutraceuti-
cals, functional foods, or pharmaceuticals.
According to the European Food Safety Authority (EFSA), it
Quality Criteria for Marine Oils for Human Consumption is difficult to give an exact recommendation for the maximum
tolerable PV and AV levels in crude oils because no literature is
The chemical composition and quality of crude oils depend on available on the relationship between oxidation values in the
both the production process and the quality of the raw crude oil and in the final oil. However, the quality of the crude
698 Fish Oils: Production and Properties

Table 3 Recommended criteria by the European Pharmacopeia (Ph.Eu) and the Global Organization for EPA and DHA (GOED) for oxidation status in
refined marine oils intended for human consumption
a b
Ph.Eur.7.0 (2011) (maximum values) GOED monograph (2006) (maximum values)
c d e f
Type of oil Peroxide value Anisidine value Peroxide value Anisidine value

Omega-3 rich fish oil (type 1) 10 30 5 20

Omega-3 rich fish oil (type 2)g 5 15
Omega-3-acid triglycerides 10 30
Omega-3-acid ethyl esters 60 10 20
Omega-3-acid ethyl esters 90 10 20 None None

oil will decide the range of application and how extensive the Carvajal, A. K., Slizyte, R., Storrø, I., Aursand, M. Production of high quality fish oil by
refining that is required. thermal treatment and enzymatic hydrolysis from fresh Norwegian spring spawning
herring by-products. Journal of Aquatic Food Product Technology, in press,
At present, no adequate international, European, or national
doi:10.1080/10498850.2013.814740.
legislation standard for origin, quality, and/or composition of Carvajal AK, Mozuraityte R, Standal IB, Storrø I, and Aursand M (2014) Antioxidants in
marine oil for human consumption is available. The European fish oil production for improved quality. JAOCS, Journal of the American Oil
Pharmacopeia (Ph.Eur) has developed standards with quality Chemists’ Society 91: 1611–1621.
criteria for some types of refined marine oils intended for Dijkstra AJ and Segers JC (2007) Production and refining of oils and fats.
In: Harwood JL and Dijkstra AJ (eds.) The lipid handbook. Boca Raton: CRC Press.
human consumption; cod liver oil, farmed salmon oil, omega- FAO Globefish Quarterly Update April 2014 – Fishmeal and Fish Oil.
3 rich fish oils, omega-3-acid triglycerides, omega-3-acid ethyl Hamm W (2009) Processing of fish oils. In: Rossell B (ed.) Fish oils, pp. 81–98.
esters 60, and omega-3-acid ethyl esters 90. In addition, both the Blackwell Publishing Ltd.
Ph.Eur and the Global organization for EPA and DHA have Jacobsen C, Rustad T, Nielsen NS, Falch E, Jansson S, and Storrø I (2009) Processing
of marine lipids and factors affecting their quality when used for functional foods.
prepared recommendations for the evaluation of oxidation sta-
In: Luten J (ed.) Marine functional foods, pp. 89–114. Wageningen, The
tus in refined fish oils and set maximum values for the quality Netherlands: Wageningen Academic Publishers.
parameters. An overview is given in Table 3. Nichols PD (2007) Fish oil sources. In: Brevik H (ed.) Long-chain omega-3 specialty
oils, pp. 23–42. England: Oily Press, PJ Barnes & Associates, Bridgewater.
Rubio-Rodrı́guez N, Beltrán S, Jaime I, de Diego SM, Sanz MT, and Carballido JR
(2010) Production of omega-3 polyunsaturated fatty acid concentrates: a review.
See also: Fish: Processing; Fish Oils: Composition and Health Effects.
Innovative Food Science & Emerging Technologies 11: 1–12.
Shahidi F and Wanasundara UN (1998) Omega-3 fatty acid concentrates: nutritional
aspects and production technologies. Trends in Food Science & Technology
9: 230–240.
Further Reading Xu X (2005) Short-path distillation for lipid processing. In: Akoh CC and Lai O-M (eds.)
Healthful lipids. Urbana, IL: AOCS Press.
Ackman RG (2006) Marin lipids and omega-3 fatty acids. In: Akoh CC (ed.) Handbook Xu X, Kittikun AK, and Zhang H (2007) Enzymatic processing of omega-3 specialty oils.
of functional lipids, pp. 311–324. Boca Raton, FL: CRC Press, Taylor and Francis In: Breivik H (ed.) Long chain omega-3 specialty oils, pp. 141–164. England: The
Group. Oily Press Bridgewater.
Aidos I, Kreb N, Boonman M, Luten JB, Boom RM, and Padt A (2003) Influence of
production process parameters on fish oil quality in a pilot plant. Journal of Food
Science 68: 581–586.
Bimbo AP (2007) Processing of marine oils. In: Breivik H (ed.) Long chain omega-3 Relevant Websites
specialty oils, pp. 77–109. The Oily Press Bridgewater England.
Bimbo AP (1990) Guidelines for characterizing food-grade fish oil. INFORM 9(5): http://www.fao.org/docrep/003/x6899e/x6899e04.htm.
473–483. http://lipidlibrary.aocs.org/processing/marine/index.htm.