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1
Department of Biological and Agricultural Engineering and
2
Department of Food Science, North Carolina State University,
Raleigh, North Carolina 27695, USA
ABSTRACT
INTRODUCTION
∗
Corresponding author. E-mail: brian farkas@ncsu.edu
81
Copyright
C 2001 by Marcel Dekker, Inc. www.dekker.com
82 ZHANG, FARKAS, AND HALE
three processes used in the commercial tuna canning industry. To develop accu-
rate mathematical models to find the optimal time and temperature conditions in
these processes, thermal properties of tuna, for example, specific heat (cp ), thermal
conductivity (k), and enthalpy (H) must be known.
The solid pack style of canned tuna has dominated the market over the years.
This style was made mostly from the albacore tuna, its delicate, white meat fetching
the highest price. However, tuna canners have been forced to use other species since
the decline of the albacore tuna off the Pacific Coast over the last 20 years, even
though a significant amount of frozen Japanese albacore is imported for canning.
Yellowfin and skipjack tuna have replaced the albacore as the main species canned
in the United States, and it appears that the skipjack has rapidly replaced yellowfin
as the largest single contributor of raw material to the tuna canning trade. Skipjack,
being darker fleshed and stronger flavored, is less valuable other than species and
little research has been done on this species.
Specific heat has been determined using microcalorimetry with internal heat-
ing and recently by means of Differential Scanning Calorimetry (DSC) (1). The
advantage of DSC is that it works rapidly and simply, much valuable informa-
tion can be obtained by a single thermogram, and a very small sample can yield
accurate results (2). This method is also used to study the thermal properties of
muscle proteins (3) and protein denaturation (4). There have been many applica-
tions of DSC in polymer science and food science. The effects of process con-
ditions on beef and vegetable protein denaturation have been investigated (4,5).
Hastings et al. (6) studied the protein denaturation of different varieties of fish
muscle.
DSC has been used to study the thermally-induced transitions of rabbit and
beef actin, myosin, and sacroplasmic proteins as a function of pH and ionic strength
(3). The effects of process conditions on beef and vegetable protein denaturation
have also been investigated. As the DSC measures net changes and can not dif-
ferentiate between the endotherms caused by the activation energy required for
denaturation and the exothermic process of aggregation, the measurements for
meat do not agree on which protein is responsible for each transition noted. Tran-
sitions around 55◦ C and 80◦ C are accepted as myosin and actin, respectively (7).
The transition around 67◦ C may be attributable to sarcoplasmic protein, connec-
tive tissue, or heavy meromyosin (7). Hasting et al. (6) reported 8 protein transi-
tions for purified cod muscle protein. Transition temperatures ranged from 27◦ C to
87◦ C.
For measuring the thermal conductivity of foods, the line source probe method
is fast and simple, and requires a relatively small sample (8). The basic theory be-
hind the probe method involves a line heat source that has been discussed previously
by Wang et al. (9). This method has been applied in many different areas. There are
research reports on such materials as soil, silicon rubber materials, and liquid chem-
icals. There are also studies on the thermal conductivity of foods. These include
frozen foods, apple juice, food powders, and fruits and vegetables (9). Recently,
thermal conductivity measurement for shrimp (10) and albacore tuna (1) have been
THERMAL PROPERTIES OF SKIPJACK TUNA 83
reported. However, for albacore, limited data is available over wide temperature
ranges. No information is available on protein denaturation enthalpy of tuna muscle.
The objectives for this study were to determine the protein denaturation temperature
and heat of fusion for skipjack tuna as well as specific heat and thermal conductivity
over temperature ranges found during processing.
Four 2-cm thick steaks were cut from whole fish and held at 24 ± 2◦ C for
thawing. After thawing, each piece was separated into four portions according to
region: loin meat, red meat, viscera, and backbone. The skin portion was discarded.
Individual portions were ground to a homogenous state by using Handy Chopper
Plus (HC3000, Black & Decker, Brockville, Ontario). Each portion was used for
specific heat measurement. Loin meat and red meat were used for protein denatu-
ration temperature measurement.
Specific heat and protein denaturation data were determined using a Perkin-
Elmer DSC 7 equipped with an Intracooler II refrigeration unit and dry box (Perkin-
Elmer Corp., Norwalk, CT). Nitrogen gas was used to flush the sample holder and
the dry box. The DSC was calibrated using both indium and dodecane.
Specific heat was determined for six individual (45–68 mg) samples of each
region using stainless steel pans (Perkin-Elmer Corp., Norwalk, CT). Samples were
scanned from 5 to 105◦ C at a heating rate at 5◦ C/min using an empty pan as the
reference. Reference pans and sample pans were balanced to within 0.1 mg. Specific
heat was calculated using the single curve method (Pyris, Perkin-Elmer Corp.,
Norwalk, CT). To ascertain the accuracy of the measurements, the specific heat of
high-performance liquid chromatographic (HPLC) grade water was measured and
found to be within ±2.4% of published values (12).
For protein denaturation temperature measurements, six individual (45–
68 mg) samples of loin meat and red meat were loaded into stainless steel pans
and scanned from 5 to 105◦ C at a heating rate at 5◦ C/min. High-performance liquid
chromatography (HPLC) water, with a weight identical to 70% of the loin meat
weight, was loaded into the reference pan. This weight was selected because it
reflected the approximate weight of water in the loin meat. Heat of fusion of loin
meat and red meat was determined by scanning six samples from −30◦ C to 20◦ C
at a heating rate of 5◦ C/min.
84 ZHANG, FARKAS, AND HALE
Whole fish were cut into four equal length pieces and held at 24 ± 2◦ C for
thawing. After thawing, loin meat was cut into 2-cm thick steaks. Viscera was
ground to a homogenous state. A controlled temperature water bath was used to
bring samples to test temperatures for determining thermal conductivity values (k
values) for the loin meat. A range of temperatures commonly found in processing
was used.
The line heat source method was used to determine the thermal conductivity of
tuna samples. A 1.25-mm diameter thermal conductivity probe (12) was used with
a Campbell Scientific 21× datalogger (Salt Lake City, UT) to record temperature
and voltage data at a sampling rate at 4 Hz. Voltage (Vr ) across a precision resistor
(R = 1.02088 ) was measured, thus the current (I) to the heating element within
the probe was determined. Another voltage measurement provided the voltage (Vi )
across the heating element. This was used to determine the energy (q) output by the
heating element. This was used to determine the energy (q) output by the heating
element. The resistance of heater wire was (Rw = 223.097 /m).
Thermal conductivity was calculated using Equation (1) below (1):
q t2
T2 − T1 = ln (1)
4πk t1
On rearrangement:
t
I 2 Rw ln t21
k= (2)
4π T2 − T1
Probe temperature was plotted against the natural logarithm of time, yielding a
linear midsection. The slope of the linear segment was then used in Equation (2) to
determine thermal conductivity.
Before each experiment, the thermal conductivity probe was calibrated using
olive oil. The experimental value obtained was compared with the published value
of olive oil and a correction factor C was obtained.
At an ambient temperature of 23◦ C, the thermal conductivity of loin meat was
measured perpendicular to the fiber of the muscle. The line heat source probe was
inserted into a loin steak sample for no more than 45 s. Ground viscera was placed
into a 30-mL beaker, into which the probe was placed for measurement.
Values of specific heat ranged from 3.192 to 3.699 kJ/kg K for loin meat, 3.180
to 3.667 kJ/kg K for red meat, 3.162 to 3.624 kJ/kg K for viscera, and 1.838 to
2.596 kJ/kg K for backbone over a temperature range of 10 to 105◦ C (Fig. 1). The
average values of specific heat over this temperature range were 3.536, 3.505, 3.446,
and 2.263 kJ/kg K for loin meat, red meat, viscera, and backbone, respectively. The
THERMAL PROPERTIES OF SKIPJACK TUNA 85
Figure 1. Mean specific heat of skipjack loin meat, red meat, viscera, and backbone over the
temperature range of 10–105◦ C n = 6. Standard deviations for this data were too small to be shown
on plot.
specific heat value for loin meat was found to be slightly higher than red meat and
viscera, and much higher than backbone. The specific heat for loin meat increased
with temperature over the range of 10–65◦ C but decreased from 65 to 80◦ C followed
by an increase. For red meat, specific heat increased up to 70◦ C and then decreased
until 85◦ C was reached. This was followed by an increase. For viscera, specific
heat increased with temperature, but had a slight decrease at 100◦ C. For backbone,
specific heat increased with temperature except at 65 and 95◦ C.
Data were statistically analyzed with the SAS GLM linear model (13). Sta-
tistical analysis showed at p < 0.05 level, a significant difference exists between
backbone and loin meat, red meat, and viscera. There were no significant differences
between loin meat, red meat, or viscera.
A comparison with the data from Perez-Martin et al. (1) study on albacore
(Table 1) showed the specific heat value of skipjack loin meat to be 9% higher than
albacore at 25◦ C. Specific heat values of skipjack loin meat at different temperatures
were also higher. These differences can be attributed to differences in composition,
especially the lower moisture content of albacore (67.3%) (1).
Figure 2 shows a typical DSC thermogram for skipjack tuna loin muscle,
and Table 2 gives three protein denaturation temperatures for loin and red meat.
86 ZHANG, FARKAS, AND HALE
Table 1. Comparison of Specific Heat of Loin Meat of Skipjack and Albacore Muscle
Red meat has higher transition temperatures than loin meat. On the basis of our
results, and assuming that tuna DSC profiles follow a similar pattern to those of cod,
the peaks on the thermogram can be assigned to be: (Protein 1) composite of the
second (major) myosin transition and the first sarcoplasmic transition; (Protein 2)
second sarcoplasmic transition; and (Protein 3) third sarcoplasmic transition or
actin transition.
The moisture content of loin meat and read meat was found to be 71.6 and
69.9%, respectively. Heat of fusion was found to be 187.76 kJ/kg K for loin meat
and was 166.45 kJ/kg K for red meat. These results are consistent with the re-
lationship between moisture content of food material and the value of heat of
fusion.
Figure 2. DSC thermogram for protein denaturation. Peaks 1, 2, and 3 represent the three protein
denaturation temperatures discussed in text.
THERMAL PROPERTIES OF SKIPJACK TUNA 87
Thermal Conductivity
Figure 3. Thermal conductivity of skipjack tuna loin muscle at various temperatures (n = 10 for
all measurement except at a temperature of 91.6◦ C where n = 1).
SAS GLM linear model (13) and showed that there were no significant differences
between k values at the different temperatures.
The thermal conductivity for loin meat was higher than the reported value for
raw albacore with a perpendicular heat flux, but was close to the reported value
with heat parallel to fibers (1). The differences can be attributed to the composition
difference of the species.
CONCLUSIONS
Specific heat values of skipjack tuna loin meat were slightly higher than that
of red meat, viscera, and backbone over the temperature range of 10–105◦ C, but
were not significantly different from red meat and viscera. This can be attributed to
the higher moisture content of loin meat. Proteins denatured at 42.56◦ C, 56.40◦ C,
and 68.69◦ C for loin meat and 43.23◦ C, 57.10◦ C, and 67.88◦ C for red meat. These
are associated with: 1) composite of the second (major) myosin transition and the
first sarcoplasmic transition; 2) the second sarcoplasmic transition; and 3) the third
sarcoplasmic transition or actin transition.
The thermal conductivity for loin meat had no significant difference from vis-
cera. Moisture content of these two portions of fish was not significantly different.
Thermal conductivity increased with temperature over a range of 33.22–91.60◦ C
except at 63.91◦ C. The decrease can be attributed to the fish muscle protein denat-
uration at that temperature range.
The values of specific heat, protein denaturation, and thermal conductivity
determined in this work will be of interest for mathematical modeling of thermal
THERMAL PROPERTIES OF SKIPJACK TUNA 89
NOMENCLATURE
ACKNOWLEDGMENTS
The authors acknowledge the financial support of Star-Kist Seafood Inc., the
United States Department of Agriculture National Needs Fellowship Program, and
North Carolina SeaGrant. In addition, the authors wish to thank Ms. Penny Amato
for her assistance with the DSC equipment and valuable discussion and Ms. Heather
Stewart for her help with the line source heat probe.
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