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Dobarganes 2000
Dobarganes 2000
Review Article
food into the frying oil modifying its quality, the inter-
cal and chemical changes in the oil or fat are expected to changes between major lipid components in fatty foods
occur as a consequence of the formation of new com- determining the composition of the finished products, and
pounds. The fried food absorbs this fat or oil of variable chemical interactions between components of the food
degradation, which contributes considerably to the quality and the frying oil giving place to non-volatile and volatile
of the dietary fat. compounds.
A high number of studies on the modifications of fats and
oils during heating and frying under very different condi-
tions has been carried out on the assumption that accept-
2 Mass transfer during deep-frying
ability of fried foods depends on the quality of the used 2.1 Major changes in food: Oil uptake
frying oil or fat. However, information on the changes in and water loss
the foods is considerably scarce, probably due to the
many different foods that can be subjected to frying and During frying heat is transferred to the food, which is
the difficulties found to replicate data given the high num- rapidly heated and covered with steam when water on the
ber of variables involved in the process. surface reaches its boiling point. The temperature of the
frying oil decreases as a result of food addition and tem-
perature inside the food increases slowly, remaining
around 100 °C, while the water is flowing from interior to
Correspondence: Carmen Dobarganes, Instituto de la Grasa
(CSIC), Avda. Padre García Tejero 4, 41012 – Sevilla, Spain.
exterior layers. Steam limits the penetration of oil through
Phone: +34 95 4611550, Fax: +34 95 4616790; e-mail: cdobar the surface to the centre of the foods, resulting a fried
@cica.es product where two characteristic zones can be defined:
(i) the dehydrated surface where the main changes take Tab. 1 summarises major changes during frying of two
place and (ii) the interior or core where temperature does frozen pre-fried foods, French potatoes and battered
not overpass 100 °C. hake, using two oils of different levels of degradation
compounds. The results for fried foods were expressed
Water loss and oil absorption in a certain food are interre- by the food weight obtained from 100 g of initial pre-fried
lated as the pressure inside the food is greater than that food. Thus, from the data shown both the loss of water
outside and limits penetration of the frying oil. The main and the net gain of oil can be directly determined by sub-
parameters influencing water loss and oil uptake are tem- traction. As can be observed, the changes depended
perature and time. It has been found that temperature has clearly on the food subjected to frying, as the final process
no significant effect between 150 and 180 °C [2] although, of frying was identical for both products. The battered
in general, the higher the temperature the lower the oil ab- hake, with lower surface-to-weight ratio, had a lower loss
sorption on the surface and, on the contrary, an excess of of total weight and moisture. However, surprisingly, the
oil absorption may result from low frying temperatures. In- amount of oil absorbed was much higher than that re-
terrelation of both variables in frying is common and thus, tained by the potato. Nevertheless, no significant differ-
the higher the temperature the shorter the time to obtain a ences were found under the conditions used due to the
fried product of similar quality. quality of the oil used [12].
Apart from the parameters established for food prepara- 2.2 Composition of used frying oils and oils
tion, water loss and fat absorption clearly depend on both absorbed by the food
food and frying oil. With respect to the food, many vari- A complementary aspect of interest is to know whether
ables affect the final composition of the finished fried there are significant differences between the frying oil in
product. Among them, food composition, in particular the the fryer and the oil retained by the food which justify the
surface structure and composition, moisture, lipid con- analytical evaluation of food lipids instead of that of frying
tent, product shape, surface-to-weight ratio, porosity, and oil or fat. There is no agreement in the literature in this re-
pre-frying treatment have been reported [3–6]. As an ex-
ample, even for a single non-lipid food, like potatoes, oil
absorption and water loss strongly depended on the pota-
to specific gravity – oil uptake being lower as the specific
gravity increases – as well as on the surface-to-weight ra-
tio exposed to the frying medium – the larger the ratio the
higher the oil absorption [7]. Nevertheless, oil uptake can
also be modified by steam treatment to remove external
oil or pre-drying [8]. On the other hand, many foods are
subjected to frying after modification of the surface by a
cover of bread or batter which modify water loss and lipid
interchange in fatty foods. Even more, small changes in
the composition of the external layers have been reported
to be essential for controlling oil absorption [9]. Thus, in
conclusion, there are many variables of control, which
make it difficult, affecting the oil content of fried foods,
which are not easy to foresee. Oil absorption can vary
from as little as 6% in the case of roasted nuts to around
40% in the case of potato crisps [10].
Tab. 1. Influence of food and polar compound level of frying oil on water loss and oil absorption. Mean of six determina-
tions. Numbers within brackets are standard errors.
Prefried food Component Before frying After frying
Initial oil* Used oil*
Potatoes Moisture 66.9 (0.34) 23.2 (0.50) 24.4 (0.43)
Lipids 4.6 (0.11) 8.5 (0.28) 8.3 (0.82)
Dry matter 28.5 29.9 28.5
Total 100.0 61.6 61.2
Battered hake Moisture 58.2 (0.93) 42.1 (0.21) 41.3 (0.26)
Lipids 6.6 (0.70) 13.5 (0.45) 14.2 (0.43)
Dry matter 35.2 35.7 35.1
Total 100.0 91.3 90.6
* Polar compounds were 4.8% and 18.6% for initial and used frying oils, respectively.
gard, even when the same substrate is considered. In Tab. 2. Total polar compounds and α-tocopherol content
some studies, similar fatty acid compositions and/or in frying oils and lipids extracted from fried potatoes
levels of news compounds in both lipids from fried Frying oil Polar α-tocopherol
potatoes and frying oils were found [12–14] while, in compounds [%] [mg/kg]
contrast, great differences between the two oils have
been also reported [15]. Frying Food Frying Food
oil lipids oil lipids
We have conducted different studies to establish differ- High oleic 5.5 4.9 535 569
ences between frying oils and oil extracted from the fried sunflower oil 16.0 15.4 10 tr
food [12, 14] by analysing total polar compounds [16], the
Sunflower oil 7.0 6.4 543 584
main groups of new compounds, i.e. polymers, oxidised
triacylglycerols, diacylglycerols, and fatty acids [17] as 19.1 18.7 185 155
well as fatty acid composition and tocopherol content. tr – traces
Fig. 1 shows the analytical scheme applied for the evalu-
ation of degradation compounds in used frying oils and in
lipids extracted from freeze-dried potatoes. As observed, in Tab. 2, showing results for polar compounds and α-to-
five groups of compounds could be quantified, i.e. triacyl- copherol contents in samples of frying oils and food lipids
glycerol polymers and dimers, oxidised triacylglycerol corresponding to two types of oils used for frying at two
monomers, diacylglycerols, and fatty acids. This detailed levels of polar compounds [14]. No differences where
analytical approach was applied to a large number of found indicating that, under the conditions applied, there
samples of fried potatoes, either crisps or French fries, was no preferential adsorption of polar compounds or nat-
prepared by industrial frying using three different oils: ural antioxidants on the food surface. Consequently, data
palm olein (PO), conventional sunflower oil (SO), and obtained from the analysis of used frying oils would be
high oleic sunflower oil (HOSO). Due to the minimum lipid representative for those obtained after food lipid extrac-
content of the potatoes, comparison between oils from tion. However, it is important to note that these results
the fryers and oils extracted from fried potatoes should refer to the oil physically absorbed or adsorbed on the
give a clear indication whether a preferential adsorption of food and, thus, new stable compounds, non-extractable
polar compounds on food surface is significant. Fig. 2 by polar organic solvents, originated through the chemical
shows the exclusion chromatograms obtained for used reactions were not included in food lipids.
frying oils and the corresponding oils extracted from
crisps. As can be observed, the profiles were practically
identical for each frying oil and the extracted oil, its coun- 3 Transfer of lipids from food to frying oil
terpart [18].
As commented on above, food quality is greatly affected
In these studies, polar compound levels were lower than by the quality of used frying fats and oils although the in-
10% in all cases although similar results were found in fry- fluence of the food being fried on the quality of the frying
ing oils with around 20% polar compounds, as observed oil may be of similar importance.
524 Dobarganes et al. Eur. J. Lipid Sci. Technol. 102 (2000) 521–528
Fig. 2. Exclusion
chromatograms of
polar compounds
in oils from fryers
and oils extracted
from crisps. Abbre-
viations: SO, sun-
flower oil; HOSO,
high oleic sun-
flower oil; PO, palm
olein.
3.1 Migration of minor compounds 6. Volatile compounds coming from strongly flavoured
foods like fish or onions can contribute to special off-
Minor compounds present in the food leaching into the
flavours.
frying oil may easily modify oil performance and quality.
Although it is not easy to find studies directed to know the Finally, apart from migration of lipids from the food into the
specific effect of minor compounds from foods, some in- frying oil, it is important to take into account that foods
teresting information can be found in general reviews which are breaded or battered may contribute particles of
[3, 15, 19, 20]. Among the main compounds contributing the surface coating to the fat, resulting in burning and off-
to modifying physical or chemical properties of used fry- flavours and increasing fat or oil degradation.
ing fats and oils the following groups stand out:
1. Amphiphilic compounds like phospholipids and emulsi- 3.2 Fat interchange during deep-frying
of fatty foods
fiers can contribute to early foaming.
2. Lipid-soluble vitamins and trace metals leaching into From a quantitative point of view, used frying oil is mainly
the frying oil inhibit or accelerate oil oxidation depend- affected by contamination with fats or lipids, which
ing on their antioxidant or prooxidant effect. migrate to the frying medium from foods. Two different
3. Cholesterol from fatty animal foods is found in veg- types of fatty foods will be considered separately: (i)
etable frying oils and can be incorporated in non-fatty natural fatty foods, i.e. fish or meat, which are normally
foods during subsequent frying operations. coated by batter or bread and are characterised by a low
4. Pigments and Maillard browning products modify the content of lipids on their surface, and (ii) the increasing
susceptibility against oxidation of frying oil and con- group of frozen pre-fried foods (potatoes, fish, vegeta-
tribute to darkening. bles, etc.) where the fat or oil is mainly located on the sur-
5. Phenolic compounds present in the foods or in added face. Lipid exchanges as well as final lipid composition
spices increase the frying oil stability. and quality might be very different in both groups.
Eur. J. Lipid Sci. Technol. 102 (2000) 521–528 Interactions between fat and food during deep-frying 525
3.2.1 Natural fatty foods Tab. 3. Quantitation of significant fatty acids before and
after frying different fatty foods in olive oil.
Great differences can be found in lipid composition de-
pending on the method of frying, type of food, and surface Sample C14:0 C18:1 C18:2 C22:6
composition, i.e. batter, bread, or uncoated food. It has Before frying
been found that battered fish absorbed less fat than
Olive oil – 76.3 8.3 –
breaded fish. The reason seems to be the rapid formation
of a crust which impedes the transfer of oil and water in Potatoes – 40.9 2.9 –
the battered food while the amount of coating in breaded Hake – 28.9 52.8 –
fish is much lower and less protective [21]. As a conse- Sardines 6.6 13.2 1.2 11.5
quence of variable fat absorption, it is difficult to foresee After frying
the fatty acid composition of the final product. The higher
Potatoes – 73.4 7.9 –
the amount of oil absorbed, the better is the final lipid
composition reflects that of the frying fat and the higher is Hake – 72.3 11.2 –
the energy density of the food. Sardines 3.1 47.9 2.8 6.0
tors to the other sensory properties typical of fried foods: one of the major groups of compounds formed at high
odour, colour, and flavour. temperatures [31].
4.1 Formation of non-volatile compounds These complex reactions have been studied in model
systems and, consequently, their extension under the
Although the main reactions contributing to the golden conditions of the frying process is unknown. On the one
colour of fried products are considered to be produced by hand, the reaction products are insoluble macromole-
protein-carbohydrates reactions, i.e. the Maillard reac- cules of difficult extraction and analysis and, on the other
tion, lipids can also play a role in non-enzymatic brown- hand, the structures and number of the new compounds
ing. Particularly, the reaction of lipid oxidation products formed through these pathways would increase enor-
with amines, aminoacids, and proteins has long been re- mously, if, as suggested, reactions between oxidised
lated to the browning observed in many foods during pro- lipids and Maillard reaction intermediates cannot be ex-
cessing and storage. cluded [32].
For those interested, some excellent reviews on the sub- 4.2 Formation of volatile compounds
ject provide complete information on the complexity of the
Lipids are the main contributors to desirable and undesir-
reactions involved between reactive groups of proteins
able flavours in fried foods. A variety of compounds con-
and oxidised lipids [19, 29, 30]. The intensity of browning
sisting in series of aldehydes, ketones, hydrocarbons,
has been primarily correlated with losses of lysine, histi-
and alcohols arise through decomposition of hydroperox-
dine, and methionine while the main reactive compounds
ides at high temperatures [33]. Even from simple model
from lipids were aldehydes, epoxides, hydroxyketones,
frying systems in the absence of food, hundreds of
and dicarbonylic compounds [29]. Fig. 3 shows the first
volatile compounds are formed which, at frying tempera-
mechanism described for non-enzymatic browning. Ac-
ture, are leaving the oil and, thus, the composition of the
cording to it, carbonyl compounds derived from unsatu-
mixture is continuously changing. However, in spite of the
rated lipids condense with free amino groups to produce
complexity of the decomposition pattern, from the propor-
imino Schiff bases which polymerise by aldol condensa-
tions of the main compounds it is not difficult to deduce
tion producing brown macromolecules. A much more re-
the fatty acids undergoing oxidative degradation [33, 34].
cent and additional mechanism has been proposed
based on the interaction of epoxyalkenals and reactive
In addition to the frying oil other important sources of
groups of proteins, which explains the formation of poly
volatiles include oxidative and thermal decomposition of
pirrolic polymers as well as volatile heterocyclic com-
food lipids, breakdown products of other main con-
pounds [30]. This is especially interesting as epoxides are
stituents of the food, and compounds produced by inter-
action of food components and/or interaction between
food and frying oil. From detailed studies and reviews it is
deduced that the difficulty rests with distinguishing the
pathway of formation of hundreds of volatile compounds
found in frying oils or fried foods [35–37]. For example,
135 volatile compounds were identified in fried bacon and
they include hydrocarbons, alcohols, ketones, aldehydes,
acids, esters, phenols, pyrazines, furans, thiazoles, oxa-
zoles, pyrroles, pyridines, etc. [37]. Such complicated
mixtures of reactive components at frying temperatures
give very complex flavour profiles and, hence, identifica-
tion of volatiles formed by interaction of frying oils and
food constituents is still a difficult task .
variables promoting formation of fatty acids. For some [5] E. J. Pinthus, P. Weinberg, I. Saguy: Deep-fat fried potato
authors, hydrolysis is the most important reaction during product oil uptake as affected by crust physical properties.
J. Food Sci. 60 (1995) 770–772.
frying [38, 15]. Nevertheless, in well-controlled laboratory
potato frying operations under many different conditions, [6] I. S. Saguy, E. J. Pinthus: Oil uptake during deep-fat frying.
hydrolytic products were minor compounds among the Food Technol. 49 (1995) 142–145.
total new compounds obtained, even if the substrate had [7] R. Guillaumin: Kinetics of food penetration. In: Frying of
a very high content of water [12, 13, 39, 40]. These results foods. Principles, Changes and New Approaches. Eds. G.
would indicate that other variables, depending on the type Varela, A. E. Bender, I. D. Morton. Ellis Horwood, Chich-
of food or not, have a much more important effect than ester (England) 1988, pp. 82–90.
moisture content [41]. [8] I. Lamberg, B. Hallström, H. Olsson: Fat uptake in a potato
drying/frying process. Lebensm. Wiss. Technol. 24 (1990)
295–300.
5 Final considerations
[9] J. F. Ang: Reduction of fat in fried batter coatings with
To sum up, interaction between food and the frying medi- powdered cellulose. J. Am. Oil Chem. Soc. 70 (1993) 619–
um during deep-frying involves many physical and chem- 622.
ical modifications in both the oil and the food, among [10] I. D. Morton, J. E. Chidley: Methods and equipment in fry-
which physical changes stand out. ing. In: Frying of food. Principles, Changes and New Ap-
proaches. Eds. G. Varela, A. E. Bender, I. D. Morton. Ellis
Main physical changes include surface dehydration by Horwood, Chichester (England) 1988, pp. 37–51.
continuous evaporation of food moisture, lipid exchanges [11] H. Alim, I. D. Morton: Deep fat frying and absorption by a
in the two directions, i.e. used frying oil absorption by the fried product. J. Sci. Food Agr. 25 (1974) 1041–1042.
food and migration of food lipids into the frying oil, and [12] M. C. Pérez-Camino, G. Márquez-Ruíz, M. V. Ruíz-Méndez,
distillation of flavour compounds. These changes are the M. C. Dobarganes: Lipid changes during the frying of frozen
main contributors to the texture and odour of fried foods prefried foods. J. Food Sci. 56 (1991) 1644–1647.
as well as to its caloric value. [13] J. L. Sébédio, A. Bonpunt, A. Grandgirard, J. Prevost: Deep
fat frying of frozen prefried foods: Influence of the amount of
Chemical reactions between main food constituents and linolenic acid in the frying medium. J. Agr. Food Chem. 38
between oxidation compounds and proteins or amino (1990) 1862–67.
acids seem to be the most important pathways for forma-
[14] N. Jorge, G. Márquez-Ruiz, M. Martín-Polvillo, M. V. Ruiz-
tion of compounds responsible for colour and flavour. Méndez, M. C. Dobarganes: Influence of dimethylpolysilox-
ane addition to frying oils. Performance of sunflower oil in
Overall, much work remains to be done to explain the discontinuous and continuous laboratory frying. Grasas y
complex reactions and interactions taking place under the Aceites 47 (1996) 20–25.
conditions of the frying process characterised by the si- [15] J. Pokorný: Substrate influence on the frying process.
multaneous action of many different variables related to Grasas y Aceites 49 (1998) 265–70.
the process, the frying oil, and the food.
[16] A. E. Waltking, H. Wessels: Chromatographic separation of
polar and nonpolar components of frying fats. J. Assoc. Off.
Acknowledgements Anal. Chem. 64 (1981) 1329–1330.
This work was funded in part by CICYT (Proyecto ALI 98- [17] M. C. Dobarganes, M. C. Pérez-Camino, G. Márquez-Ruiz:
High-performance size-exclusion chromatography of polar
0884). Authors thank M. Giménez for excellent secretari-
compounds in heated and non-heated fats. Fat. Sci. Tech-
al services. nol. 90 (1988) 308–311.
[4] E. J. Pinthus, P. Weinberg, I. Saguy: Oil uptake in deep-fat [21] J. H. Makinson, M. L. Greenfield, M. L. Wong, R. B. Wills:
frying as affected by porosity. J. Food Sci. 60 (1995) Fat uptake during deep-fat frying of coated and uncoated
767–769. foods. J. Food Comp. Anal. 1 (1987) 93–101.
528 Dobarganes et al. Eur. J. Lipid Sci. Technol. 102 (2000) 521–528
[22] C. J. K. Henry: Impact of fried foods on macronutrient in- tions. Eds. E.G. Perkins, M.D. Erickson. AOCS Press,
take, with special reference to fat and protein. Grasas y Champaign IL (USA) 1996, pp. 285–296.
Aceites 49 (1998) 336–339. [33] W. W. Nawar: Volatile components of the frying process.
[23] J. May, J. Schimp, J. Wehrauch, J. E. Kinsella: Lipids of fish Grasas y Aceites 49 (1998) 271–274.
fillets: changes following cooking by different methods. J. [34] M. C. Dobarganes, J. J. Ríos, M. C. Pérez-Camino: Rela-
Food Sci. 43 (1978) 1669–1674. ciones entre la composición de aceites vegetales y los
[24] K. L. Gall, W. S. Otwell, J. A. Koburger, H. Apledorf: Effects componentes volátiles producidos durante su termoxi-
of four cooking methods on the proximate, mineral, and fat- dación. Grasas y Aceites 37 (1984) 61–67.
ty acid composition of fish fillets. J. Food Sci. 48 (1983) [35] C-T. Ho, K. N. Lee and Q. Z. Jin: Isolation and identification
1068–1074. of volatile flavour compounds in fried bacon. J. Agric. Food
[25] F. J. Sanchez-Muniz, J. M. Viejo, R. Medina: Deep-frying of Chem. 31 (1983) 336–342.
sardines in different culinary fats. Changes in fatty acid [36] J. Pokorný: Flavour chemistry of deep fat frying in oil. In:
composition of sardines and frying fats. J. Agr. Food Chem. Flavour Chemistry of Lipid Foods. Eds. D. B. Min, T. H.
40 (1992) 2252–2256. Smouse. AOCS Press, Champaign, IL (USA) 1989, pp.
[26] J. L. Sébédio, W. M. N. Ratnayake, R. G. Ackman, J. 113–155.
Prévost: Stability of polyunsaturated n-3 fatty acids during [37] G. Takeoka, C. Perrino, R. Buttery: Volatile constituents
deep fat frying of Atlantic mackerel. Food Res. Int. 26 of used frying oils. J. Agric. Food Chem. 44 (1996) 654–
(1993) 163–172. 660.
[27] L. U. Thomson, R. Aust: Lipid changes in french fries and [38] D. Barbanti, S. Pizzirani, M. Dall Rosa: The frying operation.
heated oils during commercial deep frying and their nutri- II. Chemical and physico-chemical modifications in the oil.
tional and toxicological implications. Can. Inst. Food Sci. Ind. Alim. 33 (1994) 318–324.
Technol. J. 16 (1983) 246–53. [39] M. C. Dobarganes, G. Márquez-Ruiz, M. C. Pérez-Camino:
[28] R. M. Pozo Díaz, T. A. Masoud Musa, M. C. Pérez–Camino, Thermal stability and frying performance of genetically
M. C. Dobarganes: Intercambio lipídico durante la fritura de modified sunflower oils. J. Agr. Food Chem. 41 (1993)
patatas prefritas congeladas en aceite de girasol alto ole- 678–81.
ico. Grasas y Aceites 46 (1995) 85–91. [40] R. Arroyo, C. Cuesta, J. M. Sanchez-Montero, F. Sanchez-
[29] J. Pokorný: Browning from lipid-protein interaction. Prog. Muniz: High performance size exclusion chromatography of
Food Nutr. Sci. 5 (1981) 421–428. palm olein used for frying. Fat Sci. Technol. 95 (1995)
292–96.
[30] F. J. Hidalgo, R. Zamora: The role of lipids in nonenzymatic
browning. Grasas y Aceites 51 (2000) 37–51. [41] L. Masson, P. Robert, N. Romero, M. Izaurieta, S. Valen-
zuela, J. Ortíz, M. C. Dobarganes: Comportamiento de
[31] O. Berdeaux, G. Marquez-Ruiz, M. C. Dobarganes: Char- aceites poliinsaturados en la preparación de patatas fritas
acterization, quantitation and evolution of monoepoxy com- para consumo inmediato. Formación de nuevos com-
pounds formed in model systems of fatty acid methyl esters puestos y comparación de métodos analíticos. Grasas y
and monoacid triacylglycerols heated at high temperature. Aceites 48 (1997) 273–81.
Grasas y Aceites 50 (1999) 53–59.
[32] F. T. Orthoefer, D. S. Cooper: Evaluation of used frying oil.
In: Deep Frying: Chemistry, Nutrition and practical applica- [Received: June 8, 2000; accepted: June 26, 2000]