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Trends in Food Science & Technology 9 (1998) 336340

The impact of food


processing on
antioxidants in
vegetable oils, fruits
and vegetables
M.G. Lindley
LinTech, University of Reading Innovation Centre,
Whiteknights, P.O. Box 68, Reading, RG6 6BX UK
After microbial spoilage, oxidation leading to overt rancidity
is the second most important cause of food spoilage. Antioxidants have largely been viewed as tools in the ght
against oxidation. With increasing awareness of the importance of antioxidants in health maintenance, their retention
through food processing and storage has assumed increasing
importance. Techniques whereby fats and oils may be processed to retain the highest possible levels of antioxidants
are reviewed. Alternative processes and strategies for postharvest storage and handling of fruits and vegetables are
discussed. Further research needs that are designed to
enhance the antioxidant status of foods are proposed.
# 1998 Elsevier Science Ltd. All rights reserved

Dietary antioxidants may be nutrient or non-nutrient.


The major nutrient antioxidants are vitamins C and E,
with fruits and vegetables being major sources of vitamin
C and vitamin E compounds being found in wheatgerm,
nuts, green leafy vegetables and vegetable oils. Nonnutrient antioxidants include avonoids (found for
example in tea, red wine, onions and apples), polyphenols and terpenes. Antioxidants help to prevent the
occurrence of oxidative damage to biological macromolecules caused by reactive oxygen species. Such oxidative damage, if it occurs, may be a signicant
causative factor in the development of many human

Review
diseases. The potential role of antioxidants in preventing or ameliorating relevant disease processes has
recently been the subject of detailed critical review [1].
The focus of this paper is to discuss technical
approaches to retaining antioxidant levels in foods. As
such, it is acknowledged that success in this endeavour
does not create functional foods; foods whose antioxidant levels have been retained merely remain more
functional than those whose antioxidants have been
removed or destroyed during processing, storage and
distribution.

Technology

The protection of foods from oxygen is the basic


principle upon which antioxidant protective technologies are based. Many of these are drawn from experiences with lipid oxidation. Thus, the contribution of
food technology both to food safety and to the maintenance of high nutritional and organoleptic value
should not be underestimated.
After microbial spoilage, oxidation leading to overt
rancidity is the second most important cause of food
spoilage. To date, antioxidants have largely been viewed
as tools in the ght against food oxidation although,
with increasing awareness of their importance in
health maintenance, retention of antioxidants through
food processing and storage has assumed increasing
importance.
Maintenance of the structural integrity of foods helps
to prevent oxidative changes from occurring. In whole
food form, contact of these oxygen sensitive components with oxygen is reduced. Thus, processes that prevent exposure of antioxidants to oxygen to the greatest
possible extent have become a requirement.
Oil rening removes those components of edible oils
that can have negative eects on taste, stability,
appearance or nutritional value. Well controlled rening procedures are essential to preserve components
with favourable nutritional properties and to prevent
chemical changes in the triacylglycerols. Good rening
practices produce oils with characteristics that are
desired, such as bland avour and odour, clarity, low
colour and stability to oxidation.
Despite scientic documentation of the antioxidant
eects of selected spices, for example, rosemary, sage,
thyme, oregano, ginger, tumeric [2], only (extracts of)
rosemary are used commercially. A range of commercial

0924-2244/98/$see front matter Copyright # 1998 Elsevier Science Ltd. All rights reserved
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M.G. Lindley/Trends in Food Science & Technology 9 (1998) 336340

products is available and interest in commercial antioxidants based on other spices is increasing. Further
investigation of the eectiveness of spices may be limited by the characteristic aroma that spices tend to possess. Consequently, in many commercial products
attempts are made to extract the components responsible for the antioxidative eects, while simultaneously
reducing extraction of the aromatic essential oils [3].
However, while the use of spice extracts has obvious
attractions to food marketeers, their more widespread
evaluation and use will require more than the current
presumption of safety. The safety of spices and spice
extracts when used for this functionality is not really
proven and requires evaluation.
The addition of antioxidants to foods helps to preserve constituents of the food by preventing auto-oxidation. However, genetic enhancement of antioxidant
levels is an attractive alternative to fortication and is
increasingly feasible. The pathways controlling the biosynthesis of many secondary plant metabolites are well
documented. The importance of genetic engineering in
crop development programmes has increased in recent
years such that techniques to introduce many genes or
sets of genes into specic plant species of interest,
including major crop species, have now been developed.
Additionally, advanced breeding programmes permit
new traits to be moved into commercial crops in economically viable time-frames. Thus, there is substantial
potential for directed genetic manipulation of crops to
enhance productivity in a number of important ways,
including maximising antioxidant contents (4,5). However, it must be acknowledged that there are important
public acceptance issues surrounding the adoption of
this technology.

Processing
Processing of Fats and Oils

Fats and oils deliver energy and essential fatty acids


and are essential for fat soluble vitamin absorption.
They may contain natural antioxidants and they provide and carry fat soluble vitamins. Procedures have
evolved within the edible fats and oils industry to purify
and modify fats and oils in ways which preserve those
components with favourable nutritional properties and
also prevent chemical changes in triacylglycerols.
Harvesting, processing and storage of lipid/antioxidant-containing materials can be viewed as necessitating a series of compromises. For example, whatever level
of care taken in handling vegetable oils, from use of stainless steeel equipment, airtight packaging, refrigeration,
protection from light and the addition of antioxidants,
rancidity and all its associated deleterious changes always
occurs sooner or later. The onset of rancidity may be
delayed substantially by fortication with antioxidants,
but it cannot be stopped completely and, once deterioration starts to occur, the process will accelerate.

337

To minimize the potential for oxidation to occur,


proper handling of raw materials from their collection is
imperative. During each new handling of the raw material, it must be given the requisite protection from elements such as oxygen, heat and variably valent metal
ions. Retention of natural antioxidants present in each
specic raw material will help to extend oil shelf-life
considerably [6].
Two main oil rening methods are alkaline rening
and physical rening. Both processes employ an initial
de-gumming process to remove water, phospholipids
and metals. Alkaline rening then follows with a neutralisation stage to eliminate fatty acids. In physical
rening, fatty acids are removed by a steam distillation
step. There are limitations to both processes; alkaline
rening results in relatively low yields and large quantities of liquid euent, while physical rening employs
higher temperatures. The alkaline rening conditions
benecially remove several impurities, including oxidised components, trace metals and colour. Further
removal of impurities, along with removal of aatoxins
and some pesticides, may occur during the bleaching
process. During physical rening, volatile components,
including o-avours, pesticides and polycyclic aromatic hydrocarbons may be removed [7].
Many of the procedures used to help preserve antioxidant levels in foods, particularly physical control
procedures, involve adoption of good manufacturing
practices. These imply the use of stainless steel equipment, careful de-aeration at less than 100 C before
heating to the nal stripping temperature, the use of
oxygen-free steam, and strict control of trace element
contents of feedstocks [7]. However, with the goal of
minimizing oil oxidation, it is not merely sucient to
ensure high antioxidant contents. For example, studies
with virgin olive oils have shown that even with high
antioxidant contents, oil stability is decreased if the
initial peroxide value is high [8]. This demonstrates the
importance of ensuring that all stages in the harvesting
and handling of oil-bearing materials utilize stringent
control of all factors which could impact on the oxidation status of the oil. In addition, the identity of all
those non-nutrient antioxidants which may be important to health is not known. When it is, processes may
require adjustment to maximize their retention.
Olive oil contains many phenolic compounds whose
presence aects stability and avour. However, the
complex chemical nature of the phenolics in olive oil has
not completely been elucidated and, as yet, no standard
method has been proposed for their determination. The
system of oil extraction used is critical for total phenolics content. Continuous centrifugal methods produce
lower levels of these components than those from oils
extracted using other systems. Oil extraction using a 2phase centrifugal decanter yields olive oils with better
qualitative characteristics compared with oils produced

338

M.G. Lindley/Trends in Food Science & Technology 9 (1998) 336340

using conventional 3-phase equipment. The 2-phase


process yields oils with higher contents of polyphenols,
ortho-diphenols, hydroxytyrosol and tocopherols. Oils
prepared using a 2-phase centrifugal decanter had
higher oxidative stability. Small dierences in machinery, applied temperatures, duration of contact with
water and the volume of water employed may cause
signicant changes in total polyphenol content [9].
Conventional processing of plant-derived oils and fats
involves many dierent raw materials, products and
unit operations. The rst stage in processing is extraction of the oil. In the case of oilseeds the type of
extraction depends on the initial oil content of the raw
material. If the oil content is above 20% mechanical
pressing is usually employed; for oil contents below
20%, solvent extraction is preferred. In either case, the
majority of extractors operate continuously and counter-currently.
The rst stage in rening crude vegetable oils is
degumming using water or steam followed by centrifugation. Physical or chemical rening procedures
may then be employed (see [10], and references therein).
Chemical rening involves the addition of sodium
hydroxide followed by centrifugation. Physical rening
utilises steam to volatilise free fatty acids. After rening,
the oil is normally bleached. Bleaching not only
removes chlorophyll, but also carotenoids. Thus, this
process is a compromize between removal of materials
which reduce stability and those, the carotenoids, which
provide protection against oxidation. The nal stage of
oil processing is deodourisation using steam to remove
any remaining volatile materials.
All of these processes require large amounts of
energy, and it is this high cost which has encouraged the
development and evaluation of alternative processes
such as membrane technology in oil rening. Although
membrane technology is not yet much used in the vegetable oils industry, newly developed membranes and
process engineering developments will facilitate its further evaluation and utilization [11].
The use of membranes that are capable of separating
puried oils from the impurities present in oil-rich
extracts has received substantial attention. Potential
applications of membrane technologies to oil rening
processes have been reviewed [12]. An ideal membrane
for use in the oil-processing industry would combine the
required rejection characteristics with a high permeate
ux and long-term stability. The opportunties to save
on energy costs through the use of membrane separation processes are considerable and constitute a signicant driving force for evaluation and up-take of the
technology, but there remain many issues related to
membrane fouling, cleaning, yields and eciency which
require further research and development. Also, the
design and operation of industrial-scale membrane
reactors for use in oil processing have received little

attention. Experience gained in related industries might


prove to be applicable.

Processing of fruits and vegetables

With fruits and vegetables, many changes occur during harvesting, preparation and handling, and many of
these changes potentially impact on their antioxidant
status. Intact fruits and vegetables obviously are prone
to deleterious changes induced by respiratory, metabolic
and enzymatic activities, as well as by transpiration,
pest and microbial spoilage and temperature-induced
injury. Most such changes may impact adversely on the
antioxidant status of these products.
Identication of appropriate storage/handling conditions for fruits and vegetables is complicated by the fact
that there are non-linear relationships between, for
example, moisture content and antioxidant content.
There appears to be an optimum moisture content,
either side of which oxidation can increase quite rapidly.
Temperature control, minimizing oxygen contents and
protection from light constitute other physical procedures whose eective control can help to ensure maximum retention of antioxidants. Chemical processes
aimed at preventing adverse changes in prepared fruits
and vegetables have been practiced for many years.
Inactivation of polyphenol oxidases is one example
where inactivation of degradative enzymes can help
to maintain antioxidant status. Addition of nutrient
oxidants, particularly vitamin C, is another.
Compounds such as benzoates, sorbates, metabisulphite and polyphosphates have been demonstrated as
being capable of controlling spoilage and maintaining
quality in prepared fruit and vegetables. In addition,
preservatives that serve as antioxidants to extend shelflife of fruits and vegetables may also be shown to act
through prevention of browning, reduction in discoloration of pigments, protection against avour losses, changes in texture and loss of nutritional quality.
Their eciency depends on a range of environmental
factors such as pH, water activity (aw), temperature,
light, atmosphere and heavy metal content.
During the processing of fruits and vegetables, several
types of oxidative reactions may occur in which electrons are removed from atoms/molecules leading to the
formation of an oxidised form. These reactions cause
browning reactions, loss or changes to avour or odour,
changes in texture and loss of nutritional value from
destruction of vitamins and essential fatty acids. These
changes are important in most fruits and vegetables;
special problems arise in seed crops and lipid-containing
vegetables leading to the development of rancid o-avours and oxidation products that may have toxic
properties at high levels [13].
Four categories of chemical structures may be used to
stabilise fruits and vegetables. They are (i) free radical
chain breakers such as tocopherols, (ii) reducing agents

M.G. Lindley/Trends in Food Science & Technology 9 (1998) 336340

and oxygen scavengers such as ascorbic acid and erythorbic acid, (iii) chelating agents such as citric acid,
and (iv) other `secondary' antioxidants such as carotenoids. Of these, the most important compounds used
to stabilise fruits and vegetables are reducing agents and
certain chelating agents that are not actually antioxidants but are important in preventing oxidative
damage. Recent restriction on the use of sulphites has
highlighted the need for suitable substitutes and
although combinations of ascorbic acid and derivatives
with citric acid and other organic acids are quite eective, there remains a need for more eective combinations [14].
Packaging of fresh fruit and vegetables has been
practiced for decades to contain and protect from contaminants. An important requirement is to preserve
package contents and prevent or retard chemical
decomposition, for both fresh and minimally processed
fruits and vegetables are living tissues undergoing catabolic metabolism including respiration [15]. In order to
select appropriate packaging materials, as much information as possible must be accumulated about the nished product, including stage of maturity at harvest,
cultivar, chill injury threshold, shelf life duration target,
etc. Although some of this information is available,
much is unavailable, particularly that relating to the
interrelationships between the packaging environment
and consequent eects on nutrient and non-nutrient
antioxidants [16]. Seemingly obvious routes to maximising antioxidant status through removal of oxygen
and packaging in lm of low gas permeability actually
leads to accumulation of carbon dioxide, ultimately
inducing tissue anoxia in an anaerobic environment.
This observation demonstrates the diculties inherent
in selecting packaging procedures and materials purely
on the basis of preserving antioxidants.
Quality maintenance and/or improvement through
the use of active packaging has received recent attention, with oxygen scavenging techniques being of particular interest. Oxygen absorbent sachets, most
commonly containing iron powder or, to a lesser extent,
ascorbic acid, may be used to prolong the shelf-life of
various foods (17, 18). Alternative approaches include
incorporation of oxygen scavenging materials, such as
ascorbic acid, into the packaging itself. Vitamin E has
also been incorporated into packaging lms, from which
it may migrate into the food, so eliminating the need to
add antioxidants to the food itself [19].
New processing technologies directed towards producing stable foods following minimal treatment are
also relevant, not only for the impact these minimal
processes will have on product quality, but also on the
preservation of antioxidant status. A relevant example
may be the application of high electric eld pulses for
the treatment of fruit juices, a process that has received
attention [20].

339

Nutritional/safety implications of processes

Most studies of the impact of processing on fruits and


vegetables, in particular, have been concerned with
market quality as determined objectively and subjectively by colour, avour and texture measurements.
Data on the nutrient content and retention, particularly
for minimally processed foods, are generally sparse.
Data on ascorbic acid retention may be available. For
example, ascorbic acid is retained well in citrus juices
for about 4 weeks and only a minimal amount of
ascorbic acid is lost when juices are stored in open containers [21]. Data that determine the eects of controlled atmosphere, modied atmosphere and
refrigeration on the nutritive value of fruits and vegetables are not generally, as yet, available. Thus, the
nutritional implications of such processes, at least insofar as they relate to antioxidant vitamin retention, are
incompletely understood [22].
There are more data on the eect of processing conditions on the nutritional content of fats and oils [7].
The processing conditions under which cis-trans isomerisation, especially of linolenic acid, occurs are well
understood, and the formation of trans isomers is
slow, even under the temperature conditions (for
example, 250 C) recommended for industrial deodourisation/ physical rening. Data on the formation
of polymeric compounds during the rening process
are also available.
In intact and/or formulated foods, another eect of
heating is to increase isomerization of carotenoids. For
example, supplemental ( -carotene added to breads and
crackers before baking showed signicant trans to cis
isomerization [23], the nutritional signicance of which
stems from the observation that the cis isomer is less
well absorbed than the trans isomer [24].

Process monitoring for functions

Process monitoring for retention of antioxidants


throughout processing and storage is needed. To do so,
it may be necessary to develop rapid methods to monitor survival of the antioxidants themselves, or to measure secondary eects such as, in the case of oils,
peroxide values.

Further research needs

Most food technology needs in this area are driven by


nutrition [1]. Food technological procedures have been
developed over many years which present high quality
fats and oils whose undesirable components (avours
and contaminants) have been removed and the desirable
antioxidants retained. Techniques which lead to quality
fruits and vegetables being available for consumers are
also well established. In many respects, retention of
appropriate texture, desirable avour and appearance
correlate well with maintenance of appropriate antioxidant status.

340

M.G. Lindley/Trends in Food Science & Technology 9 (1998) 336340

However, there are areas where further work is


required, the results of which may lead to a requirement
for further food technology research into processing in
particular.
1.

2.

3.
4.

5.

6.

Generally, retention of maximum levels of antioxidants through application of appropriate food


technology processes is an appropriate goal.
However, few data exist on the nutritional value
of specic non-nutrient antioxidants. Assuming
such data are generated, there will be a need to
adapt processes to maximise their retention.
Development of membrane processing techniques
for fats and oils which reduce energy consumption, minimise degradation and maximise antioxidant status.
Research into the eectiveness of blends of antioxidants may be expected to identify possible
synergistic combinations.
The potential for spices and extracts to function
as eective antioxidants, while delivering no/
minimal avour, needs to be explored further.
Following identication of eective, avouracceptable, spice-derived antioxidants, evaluation
of their safety will be necessary.
Almost all the studies published on minimally
processed fruits and vegetables have been market
quality studies. Except for irradiation studies,
published data on nutrient content and nutrient
retention of minimally processed foods are generally sparse and are needed.
The potential safety considerations that may
result from application of minimal processes also
need to be understood.

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