Selectivity of Supercritical CO<Subscript>2 </Subscript>in the Fractionation of Hake Liver Oil Ethyl Esters

The solubility of different ethyl esters derivatized from hake liver oil in supercritical carbon dioxide was studied. A selectivity factor was used to determine optimal conditions to fractionate the ethyl ester mixture. A strong influence of solvent pressure and temperature was observed within 8.63–18.04 MPa and 40–70 °C. The lowest total solubility of the ethyl ester mixture was obtained when using supercritical carbon dioxide at the lowest density (the lowest pressure and the highest temperatures value tested). The highest discrimination against long-chain polyunsaturated fatty acids (e.g. EPA and DHA) was also obtained at these above conditions. Conversely, higher solubility and lower selectivity were obtained when solvent density increased. Considering this inverse correlation between selectivity and solubility, a single-step batch-fractionation process was designed to increase the 22:6 ethyl ester content from an initial value of 17.5% in the starting material to 55% in the final extract.     

Lipid Damage Inhibition in Hake by Active Packaging Film with Natural Antioxidants

The capacity of the natural antioxidant to retard oxidation of polyunsaturated fatty acids in hake (Merluccius merluccius) muscle was investigated. Hake fillets were packaged in low‐density polyethylene with the natural antioxidant (sample C1 = 7 mg/dm² film and sample C2 = 24 mg/dm² film) or without the antioxidant (control sample) and frozen for 12 months at ?20°C. The results confirm the efficacy of an active packaging with a natural antioxidant derived from barley husks to slow the progress of lipid hydrolysis and increase oxidative stability in hake muscle. Determination of peroxide value, conjugated dienes, free fatty acids, thiobarbituric acid reactive substances (TBARS) and anisidine value (AV) proved suitable for studying lipid hydrolysis and primary and secondary lipid oxidation over time. After 6 months of frozen storage, the TBARS levels were lower in hake packed with low‐density polyethylene with the natural antioxidant (C1 and C2) than in the control sample; at month 12, the TBARS values of C1 and C2 were lower (16 and 21%, respectively) than the control samples. AVs observed in samples C1 and C2 at month 9 were lower than those observed in the control sample at month 12. Copyright © 2011 John Wiley & Sons, Ltd.     

Estimation of freezing storage time and quality changes in hake (Merluccius merluccius, L.) by low field NMR

The potential of low field NMR (LF NMR) as a fast monitoring technique to estimate the quality of hake (Merluccius merluccius) frozen stored at -10°C for up to 6months was evaluated. LF NMR clearly detected three populations of water: water strongly bound to macromolecules (T(2b)), trapped water (T(21)) and free water (T(22)). As storage time increased, and concomitant with an increase in the T(22) and a decrease in the T(21) water populations, the water holding capacity (WHC) and apparent viscosity values decreased and the shear strength increased, reflecting the characteristic loss of juiciness and tougher texture developed by hake during frozen storage. Two mathematical models were constructed: a simple regression using the biexponential analysis of the relaxation times (T(21), T(22)) and amplitudes (A(21), A(22)) and a partial least square regression (PLS) of CONTIN analysis. Both models seemed suitable to estimate the quality of the product.     

Total volatile basic nitrogen and trimethylamine nitrogen levels during ice storage of European hake (Merluccius merluccius): A seasonal and size differentiation

Whole ungutted European hake (Merluccius merluccius) caught by trawling off the Central Tyrrhenian coast of Italy in winter and in summer were stored in ice. The dynamics of changes of total volatile basic nitrogen (TVB-N) and trimethylamine-nitrogen (TMA-N) levels during ice storage of small- (20 ± 3 cm length) and large-sized (37 ± 6 cm length) hake caught in either season were studied. The TVB-N and TMA-N levels of hake caught in winter remained low (below 20 mg and 3 mg/100 g, respectively) throughout the experiment regardless of the body size. In summer TVB-N and TMA-N levels increased sharply (P < 0.05) during ice storage and at a higher rate in small than in large fish, a fact ascribable to fish exposure to high temperatures first in the water, during trawling, and then in the fishing vessel before ice-boxing. On the basis of the results obtained in this work, it may be concluded that ungutted European hake show a clear seasonal and size differentiation of the evolution of TVB-N and TMA-N during ice storage.     

Effect of frozen storage on the quality of whole fish and fillets of horse mackerel (Trachurus trachurus) and mediterranean hake (Merluccius mediterraneus)

 Whole fish and fillets of horse mackerel (Trachurus trachurus) and mediterranean hake (Merluccius mediterraneus) were assessed for quality (physical, chemical and sensory attributes) changes throughout 12 months of frozen storage at −18 °C. The pH, expressible water (EXW), quantities of trimethylamine (TMA), dimethylamine (DMA), formaldehyde (FA), the total volatile base nitrogen (TVB-N) the thiobarbituric acid number (TBA), peroxide value (PV) and amount of free fatty acids (FFA) increased, while sensory attributes (odour, taste, texture) decreased during the frozen storage period. A comparison of quality scores between whole fish and fillets of horse mackerel and mediterranean hake showed that there were no significant differences (P>0.05) in attribute scores. There were, however, significant differences (P<0.05) in pH, EXW, TMA, DMA, FA, TVB-N, TBA, FFA and PV. Received: 19 April 1996/Revised version: 7 September 1996     

Changes on enzymatic activity and on sarcoplasmic and myofibrillar proteins of frozen-stored hake (Merluccius merluccius) pre-treated by high pressure

High-pressure (HP) pre-treatments were applied on European hake (Merluccius merluccius) followed by a frozen accelerated experiment (−10 °C). A central composite design ranging pressure levels (150–450 MPa) and frozen storage time (0–150 days) was used, being evaluated the enzymatic activities and muscle proteins. Acid phosphatase and calpain activities decreased after 150 days of frozen storage (58%/56% and 38%/56% for non-/HP-treated samples, respectively). Cathepsin B showed higher reductions (98%) for longer storage times. Furthermore, HP and frozen storage did not affect significantly cathepsin D activity, only slightly decreasing at 169 MPa. Furthermore, HP seemed to not affect myofibrillar proteins, while sarcoplasmic proteins were clearly affected by HP and frozen storage time, resulting in a reduction of about 53% or 23% for 431 or 450 MPa, respectively. Thus, HP could be used to lowering the deleterious effect of proteases on frozen European hake.     

Influence of sex, maturity and reproduction on PCB and p,p′DDE concentrations and repartitions in the European hake (Merluccius merluccius, L.) from the Gulf of Lions (N.W. Mediterranean)

The main objective of this work was to establish the influence of sex, maturity and reproduction on the contamination of the demersal fish Merluccius merluccius by organochlorine compounds. Polychlorinated biphenyls (PCBs) and p,p′DDE were quantified in muscle, liver and gonads of female and male hakes collected in the Gulf of Lions in 2004 and 2005. Observed levels appeared higher than the population of the Bay of Biscay and lower than the population of the Thyrrenian Sea. Contaminant fingerprints were roughly constant whatever the studied organ and the hake biological condition. Concentrations varied significantly according to the sex and maturity of hakes. Mature specimens were more contaminated than immature, and males presented higher levels than females. This sex effect can be linked to a lower growth rate of males, and a contaminant elimination during female spawning. Gonadal contamination depends on the importance of lipid content and increases with the maturation degree. Although the main organ of energy and PCB storage is the liver, muscle appears as the main contributor to the gonad contamination.     

Rates of free fatty acid formation from phospholipids and neutral lipids in frozen cape hake (Merluccius spp) mince at various temperatures

Hake mince was stored in frozen condition at ?5°C, ?18°C and ?40°C. Samples were withdrawn periodically, and the lipids were extracted and analysed for free fatty acid and phosphorus (P) content. The free fatty acid contents were corrected for the presence of acidic phospholipids and converted into genuine free fatty acid contents. The results at ?5°C and ?18°C showed an initial rapid surge of free fatty acid formation with a concomitant decrease in P content, followed by a second phase of slower free fatty acid generation and loss of lipid-P. At ?40°C only one phase of free fatty acid generation and loss of lipid-P was observed. The rates of the enzymic hydrolyses of the phospholipids and the neutral lipids were calculated at the three temperatures. An Arrhenius plot showed that the decrease in rate of free fatty acid formation with decreasing temperature was greater for the phospholipids than for the neutral lipids. In the rapid and more important phase, the two rates were identical at about ?12°C while above this temperature the phospholipids hydrolysed faster and below it the neutral lipids. Activation energies for the enzymic hydrolyses were calculated.