FOOD PROCESSING

ANGELA ZINNAI, FRANCESCA VENTURI*, CHIARA SANMARTIN, ISABELLA TAGLIERI, GIANPAOLO ANDRICH
*Corresponding author
University of Pisa, Department of Agriculture, Food and Environment (DAFE),
Via del Borghetto 80, 56124 Pisa, Italy

Angela Zinnai

The utilization of solid carbon

dioxide in the extraction
of extra-virgin olive oil
VOO/EVOO yield and quality as a function of extraction
conditions adopted
KEYWORDS: Olive oil, Cryogen, Solid CO2, Extractability, Extraction conditions, Mass transfer.

Abstract The impact of the addition of solid CO2 on olive oil (EVOO/VOO) production in terms of extraction yield
and chemical quality was studied at pilot scale in an industrial oil-press in two different crop seasons. The
addition of CO2,s to the fruits induces the intracellular water freezing and the consequent laceration of cellular membranes could
induce the diffusion of many cellular compounds. In the experimental conditions adopted, the addition of the cryogen to the olives
during pre-milling phase greatly increased the extraction yield (ranging from ≅ 1 to ≅ 21 %), with respect to the related control.
Furthermore, the use of solid CO2 had no negative effects on chemical composition of the olive oil, maintaining the highest quality
according to EU legal standards showed by control. Therefore, the utilization of solid CO2 as cryogen could be an appropriate
technology to improve olive oil yield and quality and increase its shelf-life.

INTRODUCTION freezing; a corresponding increase of endocellular volume

In recent years, the Mediterranean diet has become
increasingly popular, gaining widespread attention among
the nutrition and research communities (1-2) and their
unreplaceable element in this dietary style is extra virgin
olive oil (EVOO). For these reasons, extra-virgin olive oil
(EVOO) is characterized as one of the highest economic
values for vegetable oils, being the main dietary fat in the
Mediterranean countries (3-6)
One of the most important industrial handicaps of VOO
and EVOO production is the low efficiency of current
extraction techniques (7). Nowadays, several studies have
pointed out the importance of the different virgin olive oil
processing stages on the extraction yield as well as the
minor composition found in the final product and the most
used solution in oil mil for improve extraction is increase
malaxation time and/or temperature (3,7-8).
Although the important research effort devoted to find
innovative mild techniques to enhance VOO and EVOO
production (7,9-11), at industrial level the entire virgin olive
oil (VOO) process has changed very little over the last
twenty years (3).
The addition of a cryogen is a physical technology that has
been proposed for improving mass transfer processes in
food industry, mainly in wine-making technology (12). The
method is based on the evidence that the volume
occupied by the same amount of water in the solid state is
greater than that in the liquid phase. The addition of a
cryogen to the fruits induces the intracellular water
occurs and the consequent laceration of cellular
membranes (cellular break) induces the immediate
diffusion in the liquid phase of many cellular compounds.
With the aim to contribute to advance in VOO/EVOO
technology, at DAFE of University of Pisa, an innovative
VOO/EVOO extraction technology (Patent n°
ITRM20100617) involving the addition of a cryogen to the
olives (13) were developed, in order to increase the
extraction yield of an high quality EVOO. As a function of
the temperature adopted, at atmospheric pressure carbon
dioxide (CO2) can be present only in a solid (CO2,S =
carbonic snow; T < -78,5°C) and/or in a gaseous state (T >
-78,5°C) (12). Because of the direct contact between the
cryogen (carbonic snow) and the olives, the pre-milling
addition of solid carbon dioxide CO2,s (carbonic snow) to
the olives causes a partial solidification of cellular water. In
this way, it could be possible to obtain extra virgin olive oils
characterized by a greater amount of metabolic
compounds deriving from the olives even because the
relevant amount of gas (gaseous CO2,G), which evolves
during the direct contact between olives and cryogen,
decreases the amount of atmospheric oxygen diffused in
the liquid phase and then inhibits the possible oxidation of
the phenolic substances.
The main objective of the present study was to
demonstrate at pilot scale in an industrial oil-press mill, the
potential benefit of the addition of cryogen (CO2,s) directly
to olives during pre-milling phase, on the yield and quality
of the oil extracted, in order to obtain a preliminary

24 Agro FOOD Industry Hi Tech - vol 26(3) - May/June 2015

evaluation of the suitability of the new proposed
methodology for VOO/EVOO production.
Materials and methods
The study were conducted on samples of olive oil produced
from monovarietal and polyvarietal (mix) olives collected in
Tuscany during two different crop season (Table 1)
characterised by a very different weather trend during the
ripening and harvesting period for olives. In each
experimental run, olive oil samples were obtained from
homogeneous batches of olives with or without the addition
of carbon dioxide in the solid state (“carbonic snow”) and
main chemical parameters were determined, so to compare
the oil yield as well as the general quality obtained as a
function of different process conditions adopted.
Table 1. Experimental runs: origin and cultivar of the raw matter.
Determination of oil extraction yield
The extraction runs were carried out utilising a micro olive-
press (Oliomio Baby®, produced by “Toscana Enologica
Mori”, Tavarnelle Val di Pesa - Italy), which is able to mill 20÷30
kg of olives, and it was suitably modified to allow the addition
of carbonic snow directly to olive fruits and/or to their paste.
The main process steps followed by this micro olive-press
can be so schematically presented: olives properly
cleaned and washed, are poured into the receiving
hopper, where a screw feeds the crusher equipped with a
hollow knife impeller. The produced paste falls into the
lower mixer, and a helicoidally shaped stirrer promotes its
malaxation; during the malaxation phase the temperature
reached by the paste is maintained in the wished range
by a thermal regulation system (temperature sensor put
inside the olive paste, connected with a double jacket
heating system). The wished flow of the olive paste is then
sent to a biphasic decanter by a pump equipped with a
speed change gear. The decanter (4200 rpm) promotes
the separation of oil from the solid parts of olive mixed with
vegetable water plus the fraction possibly added to allow
an efficient separation of these two phases.
In each experimental run, control olive oil production was
also obtained to make comparison. In this case the
extraction process was realised avoiding any contact
between olives and cryogen. In order to allow a suitable
comparison between the results obtained in the presence
or in the absence of solid CO2 during the oil extraction
process, the olive fruits utilised in each experimental run
were suitably mixed and then the homogeneous sample
(~ 60 kg) was divided into two aliquots (30 Kg of each).
Both olives batches were processed in the same day with
(EC) or without (ET) addition of solid CO2, in order to minimize
the effect of physiological degradation of the whole fruits
during storage on the extraction yield and/or quality of the oil
obtained as a function of extraction conditions adopted
(cryo-extraction process vs conventional one).
Agro FOOD Industry Hi Tech - vol 26(3) - May/June 2015
In all the experimental run the ratio “mass of cryogen”/“mass
of fruits” was maintained constant, close to 0.2.
With the aim to avoid that the differences in the composition of
olives (i.e. cultivar and/or ripening stage as well as water content)
utilised in different experimental runs can influence determination
of the oil extraction yield, this parameter has been expressed as
“extractability” according to the following equation:
Extractability index (E) = (kg of extracted oil)/(kg of milled
olives)x % of oil inside the olives Eq. 1
Chemical analysis of oil quality
General chemical parameters, free acidity (% of oleic acid),
peroxide value (meq O2/Kg), K270 and K232, were determined
according the analytical methods described in the
Regulation 2568/1991 of the European Union Commission and
later modifications.
RESULTS AND DISCUSSION
In this paper we take in account the olives harvested in two
different crop seasons (2010 and 2014) characterised by a very
different weather trend that significantly influenced the
phytosanitary status of the fruits (14).
While the 2010 crop season in Tuscany was characterised by a
general good weather trend that allowed to obtain an increase
in the production of oil (+15,0%) if compared with the previous
year as well as a general high quality of oil produced, the 2014
has been defined as “The Black Year of Italian olive oil”. Also in
Tuscany there are multiple causes for the disastrous fall in 2014:
when the trees were turning flowers to fruit in the spring, freezing
weather suddenly turned scorching, causing the trees to drop
olives; summer was hot and humid, leading to all sorts of
problems; then in mid-September, there was a major hail storm,
knocking much of the fruit that remained onto the ground.
Finally, compounding the problems with the weather was a
troublesome infestation of a fruit fly spreading a disease known
as “olive tree leprosy”. In Tuscany, these very hard weather
conditions during 2014 season caused both a reduction of oil
production ranging from 50% to 70% than the last year and the
oil produced is characterised by a quality level lower than that
generally showed by Tuscan EVOO.
As a consequence of the worst weather trend during 2014
season the extractability index appear significantly lower than
that obtained in the same experimental conditions during 2010
crop season.
Impact of cryogen addition on oil extraction yield
In Table 2 are reported the different indexes of oil extraction
calculated for each experimental run according to eq. 1, with
Table 2. Oil extractability yield. EC = extractability yield by
innovative method (with cryogen); ET = extractability yield by
traditional method (without cryogen).
25
(EC) or without (ET) the addition of cryogen during pre-milling
phase. In order to evaluate the effect induced by the addition of
cryogen on the oil extraction yield, it was determined the
Extractability Index Variation (EIV) as the percentage of the
variation of oil extractability using CO2,s compared with the same
parameter obtained by a conventional extraction process:
EIV = (EC-ET)/ET · 100
The experimental values (Table 2) showed as the direct
addition of cryogen to the olives during pre-milling phase
could induce a general increase in the oil extractability,
ranging from ≅ 1 to ≅ 21 %.
Impact of cryogen addition on general chemical parameters.
Table 3 shows the main chemical parameters of oils
produced in all the experimental runs. Regardless the
extraction method adopted (conventional or cryo) the
values related to all the general chemical parameters
remained below the maximum limit for extra virgin olive oil
according to EU legislation (Regulation EC 1989/2003). The
impact of addition of a cryogen to the olives in pre-milling
phase did not seem have an influence on the general
quality of the produced oil.
*In relation to each couple of runs (A/1÷G/7), for each parameter values not sharing the
same letter have significantly different mean
Table 3. Oil general chemical parameters. EC = extraction with
cryogen (runs labeled with number from 1 to 7); ET = extraction
without cryogen (runs labeled with letter from A to G).
CONCLUSIONS
Even if number of experimental runs carried out until now
could appear quite reduced, the data obtained gave a
positive indication about the suitability of the new
proposed method for the oil extraction from olives so that it
will be used again during the next crop season.
Furthermore, in order to individuate the best working
conditions that could allow to obtain the best results in
olive oil production by applying the innovative extraction
process, in the next future it will be necessary to adopt
several combination of the main working parameters (i.e.
amount of cryogen/amount of olives, fruit ripening stage,
etc.) during olive oil production. In this context, also the
measure of the concentrations of high quality components
26
(such as phenols and aromatic compounds) diffused from
the solid parts of the olives into the lipid phase during the
different experimental runs, could be very helpful in order
to individuate, among several combinations of working
conditions, the optimal one.
Moreover, since the impact of the addition of cryogen to
the olives appear positive also when the oil extractability
Eq. 2 decreases, the application of this innovative technology
can be very useful especially when the production of the
olive oil shows an uncertain trend as a consequence of
bad weather conditions during ripening of fruits.
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