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C
FISHERIES AND MARINE SERVICE
Translation Series No. 2971
The protection of marine products from deterioration due to the oil oxidation - XIV. Application of citrus fruit
terpenes to fish products
by Kenzo Toyama, Koji Anzai, and Keizo Kikuchi
Original title: Suisanbutauno Aburayake Boshi ni kansuru Kenkyu-XIV Kankitsurui terupen no suisankako eno riyo ni tsuite
From: Nihon Suisangakukai shi (Bulletin of the Japanese Society of Scientific Fisheries), 39(8) : 891-898, 1973
Translated by the Translation Bureau( HH/PS) Multilingual Services Division
Department of the Secretary of State of Canada
Department of the Environment Fisheries and Marine Service
Halifax, Laboratory Halifax, N.S.
1974
17 pages typescript
Fee e9`71 SECRÉTARIAT D'ÉTAT
BUREAU DES TRADUCTIONS
I 31
DEPARTMENT OF THE SECRETARY OF STATE
TRANSLATION BUREAU
MULTILINGUAL SERVICES -vààe DIVISION DES SERVICES CANADA
INTO - EN TRANSLATED FROM - TRADUCTION DE
English Japanese
DEMANDÉ PAR
MAR 1 1 1974 Allan T. Reid PERSON REQUESTING ------- ----
DIVISION MULTILINGUES
AUTFIOR - AUTEUR
Kenzo Toyama, Koji Anzai and Keizo Kikuchi
TITLE IN ENGLISH - TITRE ANGLAIS
Protection of Marine Products from Deterioration due to Oil Oxidation-XIV
Application of citrus fruit terpenes to fish products
TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS) TITRE EN LANGUE ÉTRANG2RE (TRANSCRIRE EN CARACTÈRES ROMAINS)
Suisanbutauno Aburayake Boshi ni kansuru Kenkyu-XIV Kankitsurui terupen no
suisankako eno riyo ni tsuite REFERENCE IN FOREIGN LANGUAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE ,FOREIGN CHARACTERS.
RÉFÉRENCE EN LANGUE ÉTRANGÉRE (NOM DU LIVRE OU PUBLICATION), AU COMPLET, TRANSCRIRE EN CARACTÈRES ROMAINS. •
Nihon Suisangakukai shi
REFERENCE IN ENGLISH - RÉFÉRENCE EN ANGLAIS
Bulletin of the Japanese Society of Scientific Fisheries
PUBLISHER - ÉDITEUR DATE OF PUBLICATION DATE DE PUBLICATION
PAGE NUMBERS IN ORIGINAL NUMÉROS DES PAGES DANS
L'ORIGINAL
891-898 VOLUME
YEAR ANNE.E
ISSUE NO. NUMÉRO PLACE OF PUBLICATION
LIEU DE PUBLICATION
8 39 1973
TRANSLATION BUREAU NO. --- - NOTRE DOSSIER NCI
NUMBER OF TYPED PAGES NOMBRE DE PAGES
DACTYLOGRAPHIÉES
17
165673 REQUESTING DEPARTMENT MINISTÉRE-CLIENT Environment
BRANCH OR DIVISION Fisheries Service TRANSLATOR (IN(TIALS)
• DIRECTION OU DIVISION TRADUCTEUR (INITIALES) 1TH /P
YOUR NUMBER VOTRE DOSSIER N 0
05-02-74 DATE DE LA DEMANDE
SOS•200•10.6 (REV. 2/68) 71330-21-029 4533 3
UNEDITED TRANSIATI Far information nr,I -
TRADUCTION NON (VISE Information seulement DATE OF REQUEST
£19 . DEPARTMENT OF THE SECRETARY OF STATE
•-• TRANSLATION BUREAU
MULTILINGUAL SERVICES
DIVISION
SECRÉTARIAT D'ÉTAT
BUREAU DES TRADUCTIONS
DIVISION DES SERVICES
MULTILINGUES
tu
tr. 141, Ce 0 " E , o •c
• o•
Lees
E g ,6. re: p: réi
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UN
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ZD
TRA
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CLIENT'S NO. DEPARTMENT DI vIS I ON/BRANCH CITY
NO DU CLIENT MINISTÉRE DIVISION/DIRECTION VILLE
Environment Fisheries Service Ottawa, Ont.
BUREAU NO. LANGUAGE TRANSLATOR (INITIALS)
NO DU BUREAU LANGUE TRADUCTEUR (INITIALES)
165673 Japanese HH / PS MAR 11 1974
Bulletin of the Japanese Society, of
Scientific Fisheries
Vol. 39, No. 8, 1973
PROTECTION OF MARINE PRODUCTS FROM DETERIORATION DUE
TO OIL OXIDATION - XIV
APPLICATION OF CTTRUS FRUIT TERPFNES TO FISH PRODUCTS
(Received April 19, 1973)
Kenzo TOYAMA,* EDii ANZAI,** and KEizo KIKUCHI***
Citrus fruit oils, which contain more than 90% terpents, have been known . to prevent
flavor reversion in soybean oil and spoilage in fish sausaae. The authors attempted the
application of these substances to the protection of fish products from deterioration due to
oil oxidation while noting at the same time, the effect cf added citrus flavor on fish products.
Six citrus oils clifferina in the raw citrus source and the method of preparation were
tested for their antioxidative effect on fish oil. Thouah hardly effective when tested under
such severe conditions as those of the Active •Oxyzen Method, they were fairly effective
under such milder test conditions as those of the oven test at 37'C and the storage test at
room temperature. Aniong these citrus oils, lemon terpene was found lo be most practical as it is less ex-
pensive as ‘vell as satisfactorily effective. When it was applied to salted dried saury and
Shiokara, a product of half-autolysed skip jack gut with 30% salt, the lemon flavor im-
proved the impression of the products, although the antioxidative effect was not as significant
as that of BHA.
*Tokyo Univ. Fish., Konan 4, Minato-ku, Tokyo,Japan **Kyokuto Kagaku Sangyo Co., Jingumae 1, Shibuya -ky, Tokyo, Japan ***Taiyo Sangyo Co., Nishikata kamite, Koshigaya city, Saitama, Japan.
SOS-200-10-31
R,r1.= I noqq.7
to
2.
Synthetic antioxidants, which have been used widely to prevent
deterioration from oxidation of oils in fish products, as well as other
food additives have recently been considered for re-examination with
respect to their toxicity. Consequently, the replacement of those
synthetic antioxidants by natural products presenting relatively little
danger of poisoning has received increased attention. In the previous
reportl) Toyoma et al..examined the applicability of natural tocopherol
mixtures. The efficacy of the substance was higher than expected. It
was also recognized that when it was used at relatively higher concen-
trations, one obtained almost the same efficacy as with synthetic pre-
servatives. But they stated that the price was relatively high and this
factor created some difficulties in the actual application.
Generally, the flavor of citrus fruits is favored by Japanese
people. To mask fishy odors, juice and peels of citrus,fruits are often
used. When lemon peels and juice were added to soybean oil, it was
noticed2) not only that the flavor was improved but also that the oxida-
tion of unsaturated fatty acid was contained as well. In this case,
in addition to improving the smell, terpenes such as limonene and citral
are claimed to contribute to the prevention of oxidation. Also, there
is antiseptic effect in orange oil and d-limonene3'4) and they are
proven to be effective as preservatives for fish sausages.5). This
action is assumed to be the result of the oxidative products of d-limonene.
In the present experiment, we applied citrus fruits oil and p.892
its major component terpene to processed fish products in the hope that
they might prevent oxidation as well as add flavor, and we decided to
evaluate their potential uses.
Since there were only few reports on the antioxidant effects of
I
citrus fruits oils and terpenes, this éffect of these substances was
examined first with respect to fish oil. It was found out that when the
environmental conditions were relatively mild, some terpenes had a definite
efficacy. Consequently, their applications to dried salted saury and
to other fish.product were examined. The feasibility was recognized
for practical application and the results are summarized as follows.
EXPERIMENT
Refined citrus fruits oil and terpene samples:
Refined citrus fruits oils and terpenes used in this experiment
are all products from the Soda Spice Co. Six kinds different by their
raw materials and by their extraction methods, were used. The names
and the composition are'as follows. Orange (or lemon) oil:
Oil extracted by pressing orange (or lèmon) peels. More than
90% is terpenes, but most is d-limonene. Both oils are similar, but
orange oil contains linallol and lemon oil contains citral: As it con-
tains terpene aldehyde (major aromatic constituent), it is relatively.
expensive. It is a light yellôw liquid having An orange (or lemon) aroma.
Orange (or lemon) oil B:
This is obtained after the orange (or lemon) oil is treated with
60-70% alcohol at room temperature and after the major aromatic con-
stituent (terpene aldehyde) is removed. It is about 96% of the original
oil. Sesquiterpenes and others exist as 'components of terpenes, while they
are not found. in oils obtained by distillation. It is a*light yellow-
ish green transparent iiquid having an orange (or lemon) aroma.
Orange (or lemon) terpenes:
This is a portion obtained by reduo.ed pressure distillation (5--10mip)
4.
of orange (or lemon) oil at 50-600 C. It is about 90% of the original
oil and it contained hardly any aromatic constituents (terpene aldehyde).
It is a colorless and transparent liquid with an orange (or lemon) aroma.
As for the terpene component, the amount of lemonene is extremely large
and contains more monoterpene derivatives.
Antioxidant additive sample:
To compare and confirm the efficacy of the antioxidant virtue
of citrus fruits terpenes, BHA (butyl hydroxyanisole, produced by
Nikki Universal Co., "Sasuten", counaercial name), and which is known
as a typical :synthetic antioxidant in fish products, was used.
Fish oil sample:
Flatfish oil, produced in a fish meal factory ship of the north
sea was refined by treating it with alkali, after adding 5% of active
alumina, and by reduced pressure heating (Hg: lower than 5mm; filtered
at 230oC, after 30m stirring). It is used when the peroxide value
is_lower than 0.51 meq/kg , and the.acid value lower than 0.5.
Method of measuring the efficiency of antioxidant action with respect
to fish oil:
1. AOM (Active Oxygen Method):
The equipment used was constructed according to the study
report6)
given by the experts commission of the American Oil Chemists'
Society. All conditions for determination followed the recommendations
made in the report. The heating temperature at 97.8+0.2°C and the
cleaning air flow at 2.33 ml/sec were strictly observed. Although the
sample oils and terpenes (or BEA) were added to the refined flatfish
oil as alcohol solution, following the method described by MOORE et
*It is expressed by the milligram equivalent of peroxide oxygen in lkg of fat.
5.
in order to minimize the effect of alcohol addition, the concentration
of additives was adjusted so that the amount of additives was kept
at 1 ml per sample. For control, only the same amount of alcohol was
added. According to the RIEMENSCHNEIDER'S method,8)
about 0.1g of
samples from the sanie test tube was taken at one hour intervals, and the
AOM value was determined by the time required by the peroxide value
(measured by simple LEA'S method 9) ) to reach 125 meq/kg*. The protec-
tion factor (antioxidant coefficient) was then obtained by comparing
this value to the value of a control solution to which no terpenes or
BHA had been added.
2. Oven test:
The sample oils were prepared by adding an ether solution which
contained a calculated amount of refined sample oils and terpenes (or
BHA), to refined flatfish oil samples, Using the LEA'S method9) , about
2.2g of prepared sample oils were taken into small cylindrical cups
(lcmxlcm). More than ten from each section were prepared. The change _
of peroxide value9) was studied while storing them in a constant temper- p.893
ature bath at 37+ 1°C. In the case of very volatile additive material,
to avoid the possibility of reaction among substances while storing,10)
ail the samples were stored in a large petri dish, separately by section.
3. Experiment of storing at room temperature.
50 ml of the same sample oil used in the oven test was taken into
a beaker and left at room temperature (average 23°C) avoiding direct sun-
light. The peroxide va1ue9)
and oxidized acid va 1ue11) were determined
at appropriate intervals. To minimize errors by selectiveness, the sample
oil was mixed thoroughly every time when it was taken for determination.
*Refer to the footnote on the previous page.
1
Color
Odor
6.
Prearation of dried salted samples and experimental method:
As in the previous report,1)
using a 16 hour soaking method,
dried salted materials were prepared from fresh frozen saury, Calobis
sira (BREVOORT). After cutting off the heads, the fish bodies were
open flat, and most of the guts and bones were removed and washed by
water. They were soaked for 16 hours in 7% salt water. A calculated amount
of terpenes (or BHA) was dissolved in alcohol. Each 2m1 of it were
added to 11 of previously described salt water, while stirring. This
was used as dispersion solution. After the completion of soaking, the
samples were washed briefly and dried under the sun for two days (total
drying time was 13 hours). They were analyzed when the water content was
about 50% and stored at room temperature. With one portion of the samples,
instead of adding terpenes to the salt solution, a 10% terpene alcohol
solution was gently sprayed on the surface of the samples before they
dried, to evaluate the effect.
The results of the experiment aiming at determining the efficacy
of terpenes on the samples were evaluated in a sensory fashion and by
peroxide value 9) of oil extracted by ether (16 hours of extraction by
Soxhlet method) as done in the previous report. Although the standard for
sensory evaluation is exactly the sanie as in the previous report, it is shown
in Table 1.
Table 1. A conventional rule proposed for expressing the orranoleptically appraised grade
of deterioration as integer* for fish products.
3 4 5 6
Normal Slichtly Yellow . Sornevshat Reddish. Reddish yillow reddish yellow brown
Normal Slightly Rancid Stroncly — — - ranciii rancid ,
** The greater the integer indicating the deterioration grade, the higher the decree of rancidity
and rustinc.
7.
ration of "shiokara"(salted fish guts)and experimental method:
The internal organs of bonito were .cut open. Undigested food
residues were removed and 30% of salt added after washing. After leaving
it.overnight, the sample was prepared by chopping with an electric chopper,
after the water was removed. 300g at a time of this sample was put in a
500m1 conical flask, and cured by leaving it at room temperature (20°C) avoid-
ing direct sun light. A calculated amount of the sample terpene was added
to the immediate material and was mixed by shaking, prior to the procedure
described previously. While curing, once every day during the first week,
then once in a while, the material was stirred by -shaking the flask. The
efficacy of terpene_on the sample material was evaluated in a sensory way,
for its taste and flavor. At the same time, the peroxide value and
oxidized acid value 11) of the ether extraction (after an addition and mixing
of anhydrous sodium sulfate to the samp?e, at the rate of-6 times its
quantity, the extraction by Soxhlet method was conducted for 16 hours) were
determined and examined.
Method of determining the solubility of antioxidants in terpenes:
This was done according to the method applied by Toyama et al. 12)
for the solvent. First a terpene sample was placed in a large test tube.
Excess antioxidants were added and dissolved thoroughly by stirring at room
temperature for 30 minutes. After leaving it for five minutes, a part of
supernatant was filtered quickly. Then the antioxidant was quantitatively
determined by diluting that part in alcohol of a certain quantity. BI-IA.
was determined by the 2.6-dichloroquinone chloroimide method,l3) and BHT
was determined by the 2-2'7dipyridyl method.14) In these cases, it was
confirmed prior to the analytical procedure that there was hardly any
effect on the determination, caused by a minute amount of coexisting
terpe.nes.
8.
RESULTS AND DISCUSSION
Assa of the antioxidant efficacy of refined oils and of terpenes on
fish oil;
Prior to application of refined citrus fruits oils and terpenes to
fish processed products, the efficacy of these substances on fish oil was
assayed.
1. Evaluation by AOM.
The effectiveness of the addition of citrus fruits oils, oil B
and terpenes to refined flatfish oil was tested by AOM, adding low con-
centration (0.02%) and high concentration (0.10%) respectively. The
results are shown in Table 2. ..A,gainst the expectation, in every case,
Table 2. Antioxidative efficacy of citrus fruit oils and terpenes in refined flat fish oil (evaluated by Active Oxyten Method).
Sample No.
Citrus fruit terpenes and oils Protection Kind Concentration stabilities factor
1 Control 2 .. • Orange oil -
3 u e
4 Orange oil B* 5
6 Orange terpene
7 ii
8 Lemon oil 9
10 Lemon oil B*
11 u y
12 Lemon terpene 13
hr. 0 5.3 1.0 0.10 - 53 - 1.0 0.02 5.6 1.1 0.10 5.3 1.0 0.02 5.6 1.1 0.10 5.0 0.9 0.02 5.3 1.0 0.10 • 5.2 1.0 0.02 - 5.2 1.0 0.10 5.7 1.1 0.02 - 5.1 1.0 0.10 5.0 0.9 0.02 5. 2 1.0
* Oil B is the residaal frac:ion of citrus oil after its essential components were removed with dilute.d alcohol.
hardly any effect was recognized. The kinds of raw material or the method
of preparation seemed to have no relation to their effectiveness. Also
there was no relation between the results and the difference in concentra-
tion of the substances. In some cases, a lower concentration seemed to
9.
have more effect but the difference was very small and no significant re-
lation could be found.
This fact shows that the major aromatic constituents (terpene
aldehyde etc.) which exist in relatively large amount in orange (or lemon)
oil and other substances (hydrocarbons and totopherol and so on) do not
have any more antioxidant effect or helpful effect to antioxidant action
than terpenes do. In addition to the above fact, as the price of the oils
is more than ten times that of oil B and of terpenes, these refined citrus
fruits oils themselves are eliminated by the following experiments.
2. Evaluation by oven test.
The evaluation of the effectiveness of antioxidants by AOM does
not necessarily agree with the results of actual storing trials, because
under such severe experimental conditions as high temperatures ventilation,
oxidation develops rather quickly in samples with higher degrees of un-
saturation such as in the case of the fish oil. In the previous paragraph,
there was hardly any antioxidant power recognized in.citrus fruits oils
and terpenes. It was considered that on account of such experiment con-
ditions, no clear results were shown,asthe antioxidant power of terpenes
was relatively weak. Therefore the effectiveness of antioxidant power of
oil B and of terpenes on refined flatfish oil was examined by oven test
which represents relatively mild experimental conditions when compared with
AOM. The results are shown in Figure 1.
In this case also, there was hardly any effect shown by oil B and
terpenes, even by BHA, for a period of up to one week of storage, jun gp in
the control samples. Hereafter, effects gradually started to appear, and about
two weeks later, marked effects were finally recognized. .
10.
Pib. 1. Antioxidativic efficacy of citrasfruit oils and terpenès in refined flat
fish oil (evaluated by oven test ae37`C), \\'here, O Can:rol (No. 1^), _-,Le,non oil 13 0.101,0 (No. 15), t. ier•ionterpene 0.10;; (No. 16). M. Orangeoil B 0.10% (No. 17), G Orange ter-penc 0.10% (No. 18), E? Orange :er-pene 0.02% (No. 19), and © BKA I0.02% (No. 20).
But the effects were inferior to thoseof BHA. The effect of oil
B was inferior to that of its corresponding terpenes. These results in-
dicate that the antioxidant power of citrus fruits terpenes is weaker
than expected.
3. Evaluation under room temperature storage.
The antioxidant power of oil•B and terpenes was fairly recognizable in
the oven test. Even with this method the experimental conditions are more
rigorous than actual storing conditions. Therefore there is a risk of mis-
calculating the correct evaluation when fish oil is the substrate. There- p.895
fore one portion of the sample oil prepared for oven test was stored at x'oom."
temperature and the antioxidant power of added terpenes was examined. The
Kind
21 Control 22 Orange oil B 23 Orange terpene 24 Lemon oil B 25 Lemon terpene 26 Orange terpcne 27 BHA
0 0.10 0.10 0.10 0.10 0.02 0.02
Sample No.
Additives After 5 days
Conc. (Pffi/) meg/kg 16.51
After 6 days
Conc. Method Ôdor c°1°r* 150V Odor Color* pov I II , I II
meg/kg meg/kg 3 1 214.65 4 6 2 249.93 2 1 29.56 2 4-5, 1-2 45.07 2 1 197.84 3 5 1-2 330.66 2 1 190.66 1** 5 1-2 202.52
2 1 28.89 1** 4-5 1 34.36
2 1 144.31 1** 5 2 164.04
Antioxidative treatment ..Before storane Sample •
No. Kind
o 28 Control 0 I/ 1
1 1**
. 1**
1** 1**
0.01 0.02 0.20 0.011 0.20j
29 BHA 30 Lemon terpene 31 "
32 f BHA t Lemon terpene
33 Lernon terpene
immening I/
/I
sprayed
11. results are shown in Table 3.
Table 3. Antioxidative efficacies of citrus fruit terpenes in refined fiat fish oil when allowed
to stand in room temperature.
After Alter 16 davs 24 days (POV) (POV) mea/kn meq/kg 68.71- 97.84 45.10 76.99 40.20 66.56 46.75 73.07 45. 1 0 72.17 58.80 • 79.13 59.06 86.48
Alter 38 days
(POV) (0A*) meq/kg % 401.17 3.89 186.60 1.46 165.93 1.43 174.74 1.72 176.26 1.52 301.40 2.84 123.35 0.91
After 45 dvas (P0V) meg/kg 504.03 281.61 177.22 259.23 250.65 384.90 151.75
Aftu 52 days
(POV) (0A*) meq/kg % 577.81 7.70 380.21 4.07 4'01.70 4.39 351.83 3.77 343.99 3.48 491.08 4.13 257.77 2.62
* Oxidized acid.
As expected, it was proven that oil B and terpenes showed distinctive
power as antioxidant when used at relatively high concentration and at
room temperature. Although there was no difference in effectiveness be-
tween oil B and terpenes, from the viewpoint of the extracting method
terpenes have less possibilities of containing tocopherol and other sub-
stances than oil B, and the effectiveness was slightly better for lemon
terpene. Thus only lemon terpene was used in the following experiments.
The efficacy of lemon terpene on dried salted saury.
According to the results in Table 3, the efficacy of lemon terpene
is good enough to be used with fish products although it is inferior to
that of BHA. The experiment was conducted to prevent deterioration from
oxidation of oil in dried salted saury, using lemon terpene. The results
are shown in Table 4. Table 4. Protective efficacies of lemon terpene %:ith or without BHA for fat-oxydative
deterioration of salted-and-dried saury.
I: Abdominal cavity wand. II: Ventral tin. ** Having lemonish odor.
12.
At the end of the preparation, the control sample was already
orange yellow in the wall area of the abdominal cavity. Samples treated
with lemon terpene were light yellow in color as the samples with BHA,
and a good lemon flavor was also detected. But when oil was extracted, the
peroxide value was higher than expected, although it was generally lower
than that of the control sample and no effective antioxidant power such
as in BHA was recognized. After six days of storage, the control sample
showed general oil burn signs caused by oil oxidation, but the samples
with lemon terpene were in relatively good condition although • less
well preserved than the samples treated with BHA. Although these results
are similar in trend to the results of the experiment with flatfish oil
at room temperature, the addition of lemon flavor definitely improved the
quality impression of the product and therefore yielded results beyond
expectation. As the samples treated with both BHA and lemon terpene showed
a better appearance and state of oil than the samples treated with BHA only, p.896
the possibility of combined use of these two substances was expected. Al- —
though the concentration of the additive was relatively high, the samples
treated with lemon terpene by spraying, showed good result. Therefore, it
is considered that the use of citrus fruits terpenes with processed fish
products is hopeful enough.
The efficacy of lemon terpene on "shiokara". (salted fish guts)
It has been reported15)
that in the production of "shiokara", when
fish gut rich in oil was used, to keep its flavor and color, oxidation must
be controlled, and the strong efficacy of BHA has been recognized. When
"shiokara" is uncooked, it is considered16)
that prevention of poisonous
peroxide formation is more important than with other processed fish pro-
ducts. At present, the law does not allow the use of synthetic antioxidant.
As their odor is so strong and distinctive, peels of "yuzu" (e P.nd of
citrus fruit)* are often added in some homes. When these matters are
considered, "shiokara" is most suitable among other fish products to be
cons idered for lemon terpene application. The actual application of
lemon terpene on "shiokara" made from bonito gut was examined. The re:- _
sults are shown in Table 5.
Table 5. Antioxidative efficacies of lemon terpcne on the Shin Icara.* .
Sm le C.one. of After 10 days After 30 days After 50 days After 30 days lemon No. tcrpene Odor • POV OA** POV OA** POV OA** POV OA** Odor - ------ Taste -
% meg/kg ./ /0 meq/kg % .meq/kg . % mcq/kg % ----- - ---
34 0 Fishy 22.84 1.02 12.19 1.56 8.68 1.62 4.36 2.41 Fishy Wild .
35 0.1 Slightly 21.86 0.76 18.68 • 1.55 5.93 • 1.53 6.06 j..26 Slightly Mild fishy fishy • -
• 36
0.2 Slightly 33.67 0.79 9.44 1.85 6.2.8 1.15 6.42 j .85 Slightly Slightly lemonish lemouish harsh
. . ...,„ .,, .
37 0.5 Lemonish 24.27 0.49 10.24 1.49 6.20. 0.66 4.44 1,13 Letnopish Slightly .' - • astringent •
38 1.0 Strongly 14.2$ 0.57 . 6.65 1.51 5.44 1.30 3.31 0,72 f.,empmish . /".striageut lemonish ' •
* Partly autolysed skipjack gut with 30% of salt.
** Oxidized acid. •
Although the efficacy of lemon terpene with respect tp eontrol
of oxidation in oil was very clear, there were questions about the improver
ment of flavor, depending on the amount of terpene used.
With respect to the condition of extracted oil, although some
changes in the quantities of oxidized acid were observed during the curing
period, this quantity was generally lower in the portion treated with lemon
terpene than in the control portion. The antioxidant effect pf lemon
terpene was clear. The peroxide value was low in every case eyen in the
,control portion to which no lemon terpene had been added, and Phe çoncenr
tration did not rise enough to be considered poisonous. During the pro- , -
cess of curing, the value even seemed rather to decrease. This wap the
*Bracket is a translator's note.
14.
result of enzyme action during the curing process. Already Fulcuda15) re-
ported that the peroxide value of oil obtained from "s.hiokara "(made
from viscera of "buri", Seliola quinqûéndiâ.ta) by extraction after dis-
tillating and drying while heating, was about 30 meq/kg after 30 days of
curing, regardless of the application of antioxidants and that it decreased
after that time. This tendency agrees with the results of.this experiment,
Accordingly, if consideration is given only to the formation of peroxides,
the preventing effect in "shiokara" becomes less meaningful, but the
fluctuation of peroxide value between curing and consumption should yet
be examined.
As shown by the results of sensory examination concerning the
flavor of "shiokara" after curing, as the concentration of lemon terpene
used increaseq,the lemon flavbr remains strong and the smell of raw fish
fades; generally the flavor creates a soft impression: At.higher concen-
tration, however, the impression was not always satisfactory. The taste
of the portion (No. 35) treated with a low concentration was good, but in
the portion with a higher concentration, an astringent taste increased-with
the concentration and it was not considered satisfactory. The portion (No.
38) with highest concentration particularly had an irritating aftertaste and
showed the unsatisfactory effect of overuse. By reviewing this experiment,
fairly good results were obtained from the portion with an addition of 0.1%.
in actual application, the best results may be expected when a 0.1% or a
l.ower concentration of lemon terpene is added.
Solubility'of antioxidants in citrus fruits'terpèiies
It was accidentally confirmed in this experiment that BHA and BHT
dissolved easily in citrus fruits terpenes. Therefore the sQlubility of
these antioxidants in lemon terpene was determined. The solubility of BHA
p.898
15,
was 14.05 at 21.0°C and that of BHT was 45.82 at 19.3 °C. As already
described, citrus fruits terpenes are natural and considered haLuiless.
This character shows great possibilities for use as carrier and solvent
when adding BHA and BHT which are employed widely at present for fish
processed products.
CONCLUSION
From the results of the experiments described above, it was
confirmed that citrus fruits terpenea have efficacy in preventing oxida-
tion, and whey they are used they also add a distinctively pleasant
flavor to the products. Although it was not recognized in this experi-
ment, it was reported that d-limonene, its major constituent had an an-
tibiotic power, So in the future, the selection of the products for whiCh
it should be used and other problems of practical application must be con-
sidered.
Recently, the components of refined citrus fruits oils have been
examined in detail, and it has been reported they they contain traces of
many kinds of terpenes, sesquiterpenes and oxygen containing compounds. In
the present report, although the refined oils and their fractions pro-
duced commercially were used as •such, in the future, the effect of theee
substances coexisting in relatively small amounts and the confirmation of
their antioxidant power should be examined.
SUMARY
The use of refined citrus fruits oils and terpenes with fish pr9 -
cessed products was considered. Six samples, varying in materials and
tracting methods were examined with respect to their antioxidant power, first
on fish oil. Although no efficacy was recognized under severe environmental
16.
conditions as in AOM, fairly distinctive results were recognized in the
oven test at 370 C and in the room temperature storage test. Lemon ter-
pene was selected for its composition and price, and applied on dried
salted saury and "shiolcara" made from bonito gut. The antioxidant power
was relatively weak, but it gave a lemon flavor to the products and improved
their appearance.
We would like to express our thanks to Kyokuto Kagaku Sangyo Co.
for their assistance, to the Nikki Universal Co. for donating BHA, to.Mr.
Hisamitsu Ashida, fruits essence research director of the Soda Spices Co.
for donating citrus fruits terpenes and giving knowledge about them, to
Mr. Toyokazu Niimi of the Ninben Co. for donating "shiokara" material and
for giving advice, and to Mr. Toshi Wada, studeizt at the Tokyo University of
Fisheries for helping with the sensory test of "shiokara".
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