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Oil Production From Sardine Sardinops Sagax Caerulea Producci N de Aceite A Partir de Sardina Sardinops Sagax Caerulea
Oil Production From Sardine Sardinops Sagax Caerulea Producci N de Aceite A Partir de Sardina Sardinops Sagax Caerulea
Oil Production From Sardine Sardinops Sagax Caerulea Producci N de Aceite A Partir de Sardina Sardinops Sagax Caerulea
Sardine (Sardinops sagax caerulea) oil was rened and the fatty acid composition as well as the physical and the
chemical quality variables were monitored. The rening of crude sardine oil was carried out in three stages: alkali-
rening, clay-bleaching, and steam-deodorizing. Results show that the rening process signicantly improved
(p 5 0.05) the chemical quality of the oil, by decreasing its peroxide value (from 10.05 to 0.81 meq/kg), p-anisidine
value (from 3.67 to 1.63 mmol/kg), and free fatty acids content (from 0.21 to 0.052% as oleic acid). The oxidative
stability increased from 10.39 to 17.55 h (using Rancimat at 608C, and 7 L/h air ow). These values are within the
acceptable standards for edible sh oils. No signicant dierences (p 5 0.05) were observed in fatty acids
composition. The notable improvement in the physical properties of rened sardine oil produced high quality sh oil
in terms of color (golden yellow) and odor (odorless).
Keywords: fatty acid composition; sh oil processing; marine oil; n-3 PUFA; sardine
En este trabajo, el aceite de sardina (Sardinops sagax caerulea) fue renado y la composicion de acidos grasos, as
como las variables de calidad fsica y qumica fueron monitoreadas. La renacion del aceite crudo se llevo a cabo en
tres etapas: Neutralizacion con alcali, blanqueado con tierras y desodorizacion con vapor. Los resultados mostraron
que el proceso de renacion mejoro signicativamente (p 5 0,05) la calidad qumica del aceite, por la disminucion de
su valor de peroxido (de 10,05 a 0,81 meq/kg), valor de p-anisidina (de 3,67 a 1,63 mmol/kg) y el contenido de acidos
grasos libres (de 0,21 a 0,052% como acido oleico). La estabilidad oxidativa aumento de 10,39 a 17,55 h (utilizando
Rancimat a 60 8C, y 7 L/h ujo de aire). Estos valores estan dentro de las normas aceptables para los aceites
comestibles de pescado en terminos de color (amarillo dorado) y olor (inodoro).
Palabras clave: aceite marino; aceite de pescado renado; composicion de acidos grasos; n-3 PUFA; sardina
totaling 576,443 tons/year, which represents 37% of located in Yavaros Sonora, Mexico. The crude
the world sardine shery. About 70% of this sardine is sardine oil was transported to the laboratory in 4 L
processed by plants producing sh meal, which has amber glass sealed containers at 08C, and stored
commercial importance as raw material in animal feed until analyzed and processed at 7308C in custom-
that produce 10,000 tons/year sh oil as by-product made portions ushed with nitrogen. All reagents
with little or no commercial value (CONAPESCA, (analytical grade) and the solvents (chromatographic
2007, http://www.conapesca.sagarpa.gob.mx/wb/cona/ grade) were purchased from Sigma-Aldrich (St.
cona_anuario_estadistico_de_pesca). Louis, MO).
According to Gamez-Meza et al. (1999), the most
abundant fatty acids in crude sardine oil, caught o in
the Gulf of California are: palmitic (19%), palmitoleic Sardine oil rening
(8.5%), stearic (6%), oleic (14%), eicosapentaenoic Rening of crude sardine oil was carried out in three
acid (EPA, 20%), and docosahexaenoic acid (DHA, stages: alkali-rening, clay-bleaching, and steam-
13%). Therefore, sardine oil can be considered an deodorizing. These stages were conducted at labora-
important source of n-3 PUFA, because EPA and DHA tory scale in glass equipment following procedures
together represent one third of the total fatty acids and recommended by Bimbo (1998). The oil yield on
90% of total polyunsaturated fatty acids (PUFA). each stage was determined by weight during the
The chemical and physical properties of edible oils rening process. In the alkali-rening stage, 1 kg of
depend primarily on the composition of the raw crude oil and 16 g of a 4.2 M NaOH solution were
materials and processing temperatures. Normally, mixed at room temperature with continuous stirring
sardine processing is carried out by heating the sh in (300 rpm) for 15 min. Subsequently, the system was
large, continuous cookers at 951008C for 1530 min heated to 658C to break the emulsion and facilitate
(Bimbo, 2007). The crude oil obtained by traditional soap removal by ltration. Bleaching was carried out
heat processing tends to be dark in color and contains a at 908C using partial vacuum (15 mbar) and 3.0% of
large amount of impurities. Therefore, rening steps acid-activated diatomaceous earths (Tonsil optimum
including neutralization, bleaching, and deodorization 320 FF, Sud Chemie de Mexico). The spent earths
are necessary. However, the high temperatures and were separated by ltration after of 30 min of
chemical treatments utilized during these steps may agitation. Deodorizing was performed at 1408C for
cause isomerization of polyunsaturated fatty acids 5 h under a pressure of 1.5 mbar in a laboratory
(PUFAs) such as EPA and DHA, producing trans distillation unit that consisted of a 2000 mL round
isomers with a concomitant decrease in its nutritional bottom boiling ask with three outlets. A continuous
value (Berdeaux et al., 2007). It is generally recognized stream of water steam (5% w/w oil) was directly
that high temperatures inuence sh oil deterioration injected to the oil and the volatile compounds were
and can accelerate lipid oxidation. When sh oils condensed using double cold trap (748C). During
oxidize, they produce unstable intermediary com- cooling of the oil, 0.2 g of ter-butylhydroxyquinone
pounds, such as free radicals and hydroperoxides, (TBHQ) and 0.1 g of an aqueous citric acid solution
which are susceptible to further decomposition into (150 g/L) were added to 1 kg of oil as antioxidant
products such as aldehydes and ketones (Moriya et al., agents. A sample with no-antioxidant added was
2007). These decomposition products adversely aect previously withdrawn to evaluate its oxidative
avor, taste, nutritional value, and the overall quality stability.
of sh oils (Bimbo, 2007). The aims of oil processing are
to maximize yield while maintaining high quality and to
produce highly stable oils by eliminating undesirable Sardine oil quality
compounds. The high levels of PUFAs in sardine oil are The physical and chemical quality of the crude sardine
subjected to rapid and extensive oxidation by exposure oil during the dierent stages of the rening process
to high temperature, air, or light (Sang & Jin, 2004). was evaluated according to the ocial analytical
Consequently, it is necessary to control and monitor methods (AOCS, 1998).
this process in order to avoid these collateral eects.
For this reason, in this work crude sardine (S. sagax) oil
was rened and the physical, chemical quality, and the Physical quality
fatty acid composition during the alkali-rening, The crude sardine oil physical quality was monitored
bleaching, and deodorization stages were monitored. through the rening process by measuring its density,
refractive index, and color. The refractive index and
the color were measured using the Abbe refractometer
Materials and methods
and the Lovibond1 tintometer, respectively (Cc 725
Crude sardine oil and reagents and Cc 13e-92; AOCS, 1998). Specic gravity was
Fresh crude oil obtained from sardine was provided by determined at 258C using a picnometer, according to
Productos Pesqueros Industrializados S.A. de C.V., technique Cc 10a-25 (AOCS, 1998).
CyTA Journal of Food 175
Fatty acid composition Crude sardine oil physical quality during the rening
Fatty acids of the sardine oil were converted into fatty The sardine oil density and refractive index were
acid methyl esters (FAME) according to AOCS method practically constants through the rening stages
(Ce 2-66; AOCS, 1998), and their composition was (Table 1). However, the physical aspect of the sardine
determined by GC/FID (Ce 1f-96; AOCS, 1998) in a oil was improved by a signicant reduction of the red
Varian 3400 gas chromatograph. A 100 m 6 0.25 mm coloration (p 5 0.05), mainly after the bleaching stage.
i.d. fused silica capillary column coated with a 0.25 mm The nal rened sardine oil showed a brilliant and trans-
thick lm SP 2560 (Supelco-Sigma, Mexico) was used. parent light yellow color (20A84.1R). This coloration is
Oven temperature was set at 1808C. Injector and within the standards for deodorized sh oils (Young,
detector temperatures were held at 2508C and nitrogen 1985). The color of oils is a determining factor in
was used as a carrier gas (20 cm/s). FAME peaks were quality because dark-colored oils require high-cost
identied by comparison with the retention time of the processing to achieve an acceptable light-colored product.
Table 1. Evaluation of the physical quality of crude sardine oil during the rening stages.
Tabla 1. Evaluacion de la calidad fsica de aceite crudo de sardina durante las etapas de la renacion.
Values (w/w %) are mean+standard deviation of triplicates. Values in each row with dierent superscript (ac) indicate signicant dierences
(p 5 0.05).
*Red Lovibond1 units measured with the 5.25 cm cell.
Los valores (w/w %) son la media+desviacion estandar de triplicados. Los valores en cada la con diferente superndice (ac) indican una
diferencia signicativa (p 5 0,05).
*Unidades Lovibond1 de rojo, medidas con celda de 5,25 cm.
176 J.A. Noriega-Rodrguez et al.
Table 2. Evaluation of the chemical quality of crude sardine oil during the rening stages.
Tabla 2. Evaluacion de la calidad qumica del aceite crudo de sardina durante las etapas de la renacion.
Values (w/w %) are mean+standard deviation of triplicates. Values in each row with dierent superscripts (ad) indicate signicant dierences (p 5 0.05).
*
Using Rancimat at 608C; 7 L/h of air ow rate. , not determined.
Los valores (w/w %) son la media+desviacion estandar de triplicados. Los valores en cada la con diferente superndice (ad) indican una
diferencia signicativa (p 5 0,05).
*
Usando Rancimat a 608C; 7 L/h de ujo de aire. , no determinado.
CyTA Journal of Food 177
A low phosphorus level in the crude sardine oil was saturated fatty acids (SFA) represented the most
found (1.86 mg/kg). The level reported for this element abundant oil fraction, ranging from 24.98 to 26.62
in crude sh oils varies from 5 to 100 mg/kg (Bimbo, (w/w %) of oil, followed by PUFAs, which ranged
1998). The phosphorus determination is useful to know from 20.48 to 25.02 (w/w %) of oil. The analysis shows
the content of hydrated gums. Degumming is not high levels of n-3 PUFAs (17.99 to 22.51 w/w %) in
usually carried out with animal fats and sh oils oils extracted from sardines caught out in the coast of
because they are low in phosphatides. Crude oils with the Gulf of California. The major fatty acids in sardine
values greater than 100 mg/kg require a degumming oils were 16:0, 18:1 n-9c, 20:5 n-3c, and 22:6 n-3c,
process, before the alkali-rening (Erickson, 1995). being 20:5 and 22:6 the highest of the PUFAs, which is
For crude sh oils, the recommended values for consistent with another recent report (Okada &
copper and iron were smaller than 0.3 and 0.5 mg/L, Morrissey, 2007).
respectively; whereas for rened sh oils, these values In the CG/FID analysis of the sardine oil during
should be below 0.05 mg/kg for copper and 0.12 mg/L the rening stages, trans-FA was not detected. This
for iron (Young, 1985). In this work, the levels of could be due to the maximum temperature using
copper and iron (pro-oxidants) in the crude and rened during the rening in this work that was of 1408C.
sardine oil, were below these values reported for sh According to Dinamarca, Garrido, & Valenzuela
oils (Table 2). During the rening process, copper was (1990), the use of deodorization temperatures higher
reduced by 40% and iron by 93.5%. The calcium and than 1408C probably causes a reduction in the content
magnesium levels were 1.4 and 0.34 mg/L, respectively. of EPA and DHA in the sh oil by the formation of
Rened oils must have contents smaller than 1 mg/L of trans fatty acid by thermal degradation. Fairly recent
calcium and magnesium (Erickson, 1995). Normally, studies (Fournier et al., 2007; Shativel, Prinyawiwat-
these elements are present in oils forming non-hydrated kul, Negulescu, King, & Basnayake, 2003) have shown
gums with liposoluble phospholipids. These gums are that degradation (loss) of PUFA occurred readily at
considered pro-oxidant and can aect oil stability. temperatures above 1808C, cyclization of unsaturated
fatty acids takes place at higher temperatures
(42008C), whereas triacylglycerols polymers and
Fatty acid composition dimers were found in the polar fraction of deodorized
The composition of main fatty acids found in the sh oil at temperatures higher than 2208C. Therefore,
sardine oil during the rening stages is shown in the quality of the rened oil is strongly dependent on
Table 3. The fatty acid prole of the crude oil is similar the operation conditions used during rening and
to previously reported for sardine oils (Ackman, 2005; specially during deodorizing. In this work, fatty acids
Bandarra, Batista, Nunes, Empis, & Christie, 1997; analysis did not show signicant dierences (p 5 0.05)
Gamez-Meza et al., 1999). GC analysis showed that in the individual content of these compounds except
Table 3. Fatty acid composition of crude sardine oil during the rening stages.
Tabla 3. Composicion de acidos grasos del aceite crudo de sardina durante las etapas de la renacion.
Values (w/w oil%) are mean+standard deviation of triplicates. Values in the same row with a dierent letter are signicantly dierent (p 5 0.05).
Los valores (w/w oil%) son la media+desviacion estandar de triplicados. Los valores en cada la con diferente letra indican una diferencia
signicativa (p 5 0,05).
178 J.A. Noriega-Rodrguez et al.
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