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Article history: An innovative biodegradable bio-based film packaging system has been designed to achieve equilibrium
Received 9 November 2012 modified atmosphere packaging (EMAP) of high value fresh horticultural produce through tuning the
Received in revised form 10 March 2013 packaging barrier properties combining laser micro-perforation, breathable membrane technologies and
Accepted 11 March 2013
materials. The tested commodities were cherry tomatoes and peaches. Laser micro-perforated 30 m
polylactic acid (PLA) film was used as the main bio-based packaging material. Key parameters of the novel
Keywords:
bio-based EMAP system for the selected horticultural produce were optimized in terms of performance
Bio-based EMAP
and cost reduction. Laboratory experiments were employed in order to validate the optimal design of
PLA packaging film
Biodegradable packaging
the innovative EMA package. Results from lab experiments show improved efficiency of the optimized
Fresh horticultural produce PLA based EMAP system in prolonging the shelf-life time of horticultural commodities as compared to
Cherry tomatoes non-packed commodities and commodities packed with conventional oriented polypropylene (OPP) film.
Peaches The exposure of the PLA film to the EMA packed fresh produce conditions during the shelf-life period has
negligible effect on the mechanical, physical and chemical properties of the film.
© 2013 Elsevier B.V. All rights reserved.
0926-6690/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2013.03.017
D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80 69
EMAP for the packaging of fresh fruit and vegetables dif- quality, firmness and colour of the fresh produce is still at the very
fers markedly from the modified atmosphere packaging (MAP) early stages of research and development.
designed for meat, fish, poultry and bakery goods in that produce Current applications of bio-based materials have not taken
is still “alive” and respiring. Traditional gas flushed, barrier MAP full advantage of the inherent properties of the biodegradable
packs aiming at lowering the amount of oxygen (O2 ) to slow down products that would revolutionize food packaging. An innovative
the oxidation reactions rate and the growth of various forms of aer- biodegradable bio-based film packaging system has been devel-
obic life, used in the meat industry are unsuitable for the produce oped recently to achieve EMAP of high value sensitive horticultural
industry. The films typically used in the produce industry, possi- fresh produce by combining laser micro-perforation and breath-
bly modified by appropriate perforations, offer controlled exchange able membrane technologies in the framework of HortiBioPack
for the relevant gases (CO2 , O2 , and water vapour). Moreover, they (EU Project ‘HortiBioPack’, 2008; Mistriotis and Briassoulis, 2012).
exhibit high clarity, good sealing, and anti-fog properties. The most The basic design concept and key design parameters of the novel
commonly used films for equilibrium modified atmosphere pack- bio-based EMAP system and their optimization in terms of perfor-
aging are made of low density polyethylene (LDPE) and of isotactic mance and cost reduction are presented in the present work. The
polypropylene (PP). Both plastics can be formulated into films of performance of the optimized PLA-based EMAP system was evalu-
adequate strength. In addition, both LDPE and PP are rather inex- ated experimentally. The targeted in-package conditions have been
pensive, but not biodegradable, materials (Farber and Dodds, 1995). achieved for specific cultivars of peach and cherry tomatoes under
The latter point is an enormous drawback, due to the continual ambient shelf storage conditions. As a result the produce shelf life
environmental pollution caused by non-degradable synthetic poly- under the given conditions has been extended. The experimental
mer wastes. results were also used to validate the analytical model developed
Developing and using biodegradable bio-based polymers is con- for the PLA-based EMAP design (Mistriotis and Briassoulis, 2012)
sidered as the most thorough method for resolving the serious and were compared against the results of 3D numerical simulations
plastic waste management problems and replacing fossil-oil based used for modelling the effect the optimized design parameters on
materials with materials from renewable resources. With this back- the behaviour of the EMAP system (Briassoulis et al., 2012). The
ground, the development of biodegradable polymers has been a overall performance of the PLA films used in these EMAP experi-
growing concern since the last decade of the 20th century. A ments was evaluated by measuring the evolution of some critical
variety of biodegradable polymer materials have been prepared properties of the films at the end of the shelf-life time. The evalua-
and several of them have already been industrialized (Stridsberg tion of the sensory quality characteristics and the microbiological
et al., 2002; Lindblad et al., 2002; Okada, 2002; Kricheldorf, 2004; spoilage of the horticultural produce packed with the PLA-based
Albertsson and Varma, 2002). Although significant advances have EMAP are beyond the scope of the present work as this topic has
been made with the biodegradable polymers development, they been investigated thoroughly with earlier full-scale experimental
are far from becoming substitutes for traditional fossil oil based series (D’Aquino et al., 2011a,b, 2012a).
polymers. The major reasons lay in the higher price of bio-based
polymers, the lack of international standardization and labelling
and partially, in the properties of some of these materials (e.g. high 2. Innovative design of bio-based EMAP for horticultural
hydrophilicity, poor processabilty). produce
A few studies reported in the literature show that the major
limitation in the current formulations of biodegradable poly- 2.1. Design requirements for EMAP of tomatoes and peaches
mers for applications as packaging materials is their poor barrier
properties (Shogren, 1997; Kantola and Helén, 2001). The water Two specific sensitive high value horticultural fresh produce
vapour transmission rates (WVTR) of biodegradable polymers at were considered in the framework of EU Project ‘HortiBioPack’
25 ◦ C is 20–300 g/m2 /d (depending on polymer type) is much (2008): peach (fruits) and cherry tomato (vegetables). The research
higher than that of polyethylene, which is around 1 g/m2 /d conducted allowed defining the design requirements of biodegrad-
(Shogren, 1997). The high permeability to water vapour, com- able EMAP to reduce microbiological spoilage in fresh cherry
pared to traditional synthetic plastics inhibited so far their use tomatoes and peaches as well as to preserve and prolong shelf-life
for packaging of horticultural produce, when loss of water con- through EMAP under simulated marketing conditions, i.e. 18–20 ◦ C
tent is the major factor that reduces shelf-life. This holds also and 60–65% RH. Extensive laboratory experiments (D’Aquino et al.,
for perforated films, as biodegradable films used for packaging 2012a) have shown that for given storage conditions, specific in-
of tomatoes were found to induce a much larger weight loss in package concentration values of CO2 , O2 and water vapour (WV)
the produce due to release of water, compared to a polyethylene could improve the shelf life and quality of cherry tomatoes and
package with the same perforation characteristics (Kantola and peaches.
Helén, 2001). In order to attain optimum conditions, the package Reduced levels of O2 and increased levels of CO2 (within cer-
must be specifically designed to match the handling conditions, tain limits) can conveniently prolong postharvest life and minimize
ethylene sensitivity and respiration rate of the produce to be ethylene-dependent responses of commodities prior the onset of
packed. ripening (possibly combined with hot water pre-treatment), but
Several research efforts have been carried out and work is in once the ripening process is initiated their physiological activity
progress aimed at developing biodegradable packaging materials is drastically reduced (D’Aquino et al., 2011b). Decay was gener-
for various applications, including food packaging. For example, ally higher in packages with lower water vapour permeability, due
poly(lactic acid) (PLA) is currently used as a food packaging poly- to the higher levels of in-package humidity. On the other hand
mer for short shelf life products with common applications such as in-package humidity was found to be the most important fac-
containers, drinking cups, sundae and salad cups, overwrap and tor affecting overall appearance, firmness, shrivelling, ageing. Only
lamination films and blister packages. A limited portion of this packed cherry tomatoes could maintain market quality for 28 days
research effort is dedicated to EMAP packaging systems. The devel- at 20 ◦ C. In peaches kept in atmospheres containing below 10% O2
opment of biodegradable films that are based on renewable raw and above 10% CO2 , the taste and odour were negatively affected
materials and are designed for EMAP systems for fresh produce, (D’Aquino et al., 2011a). Large amounts of unwanted substances,
meeting the design criteria of water vapour and gas barrier proper- such as ethyl acetate and a range of other alcohols and esters, were
ties, ensuring safety of the produce while maintaining the original produced in peaches kept in those atmospheres, and only in fruit
70 D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80
Table 1
Storage conditions, respiration and transpiration rates and targeted head-space EMA Package conditions (HortiBioPack; 2008).
Storage conditions Respiration rate (ml(CO2 ) h−1 kg−1 ) Transpiration rate (g(H2 O) d−1 ) EMAP CO2 (kPa) EMAP O2 (kPa) Targeted EMAP conditions
Cherry tomatoes
18–20 ◦ C 60–65% RH 12–15 4–6 2–6 15–20 18–20 ◦ C 80–90% RH
Peaches
18–20 ◦ C 60–65% RH 22–40 2–4 1–3 15–20 18–20 ◦ C 80–90% RH
stored in an atmosphere of 18–20% O2 and 2–3% CO2 taste and mechanical properties and processability are sufficient to make
odour were not negatively affected. thin films that fulfil fruit packaging requirements; its radiomet-
Transpiration and respiration are both biological processes and ric properties (transparency) satisfy the requirements of fresh fruit
the corresponding rates vary with respect to cultivars. The transpi- and vegetable packaging; its gas permeability properties are suit-
ration and respiration rates of selected varieties of cherry tomatoes able for tuning an EMAP system and is also an economically feasible
and peaches under targeted EMAP conditions were defined in the material to use as a packaging polymer (Bogaert and Coszac, 2000;
framework of EU Project ‘HortiBioPack’ (2008). The typical storage Datta et al., 1995; Sawyer, 2003).
conditions and the targeted in-package gas mixture concentrations A thorough analysis of the mechanical, structural and physical
are presented in Table 1. properties of PLA is presented in (Cocca et al., 2011; Di Lorenzo
et al., 2011). Experiments conducted at the AUA laboratory with
2.2. Designing bio-based EMAP for horticultural produce samples of PLA films exposed directly to acidic (tomato and peach
juice) and neutral (water) pH environment for two weeks showed
The most common material used in EMAP of fresh produce and no pronounced changes in their mechanical, structural, physical
vegetables is perforated oriented polypropylene (OPP), which has and barrier properties.
low permeability, acting as a barrier, with respect to relevant gases, PLA film offers selective permeability with respect to the three
namely WV, CO2 , and O2 . Therefore, the synthesis of the in-package gases which are important in fresh produce packaging, namely
atmosphere is regulated only by the size and number of perforated O2 , CO2 and H2 O (WV). The volume permeability of PLA films to
holes. Biodegradable bio-based polymers such as PLA and starch- CO2 is reported 0.9 × 10−17 m2 s−1 Pa−1 . The WV mass permeabil-
based polymers used for the production of food packaging films ity of the PLA films used in the present study was measured at
have WVTR much higher than the conventional OPP films. As a the laboratory by the Standard testing method ASTM-E96/E96-
result, the effect of micro-perforation with respect to WV perme- 05 equal to 1.37 × 10−11 g m−1 s−1 Pa−1 . This value is within the
ability is influenced by the permeability of the film. In the work of range of values reported by Auras et al. (2004). This increased WV
Mistriotis et al. (2011) it was shown that the effect of perforation permeability of PLA films compared to CO2 (1000 times), allows
on WV permeability decreases as the WVTR of the film increases. for regulating in-package RH by selecting a suitable surface area
On the other hand, the same biodegradable films behave as barriers of the permeable to WV packaging film without interfering with
with respect to CO2 and O2 with similar transmission rates to OPP the control of in-package CO2 concentration that is regulated only
films. This versatility of bio-based biodegradable materials offers through perforation. The O2 permeability of PLA is similar to CO2 ,
new possibilities in optimizing the design of EMAP systems for namely equal to 2.3 × 10−17 m2 s−1 Pa−1 . This suggests that, once
fresh horticultural products while it allows for an environmentally the needed perforation characteristics to ensure the proper CO2 ,
friendly disposal of the packaging waste. O2 atmosphere inside the package is established, a proper opti-
The basic design concept presented analytically in (Mistriotis mization of processing conditions may render PLA films promising
and Briassoulis, 2012) and numerically in (Briassoulis et al., 2012) material for EMAP packaging of fresh horticultural produce.
is the following: Transpiration is a more intense process producing Laser micro-perforated 30 m polylactic acid (PLA) film was
20 times larger volume of WV compared to the CO2 volume pro- used as EMA Packaging material for fresh horticultural produce
duced through respiration. If perforation is designed for regulating in the framework of the EU project HortiBioPack (2008). Laser
in-package CO2 concentration to the desired level, its effect on the micro-perforation was achieved through optimization of the laser
in-package RH is negligible due to the much higher transpiration processing parameters to enable the production of repeatable
rate compared to respiration. Therefore, when a selectively perme- patterns of clear circular 200 m diameter micro-holes on the
able to WV, but barrier to CO2 , O2 covering bio-based film is used processed 30 m PLA film (Obetti, 2012).
as a packaging material in EMAP systems, the perforation pattern
can be designed for controlling only the CO2 concentration, while 2.4. Experimental evaluation of shelf-life and quality of cherry
the area of WV permeable packaging film surface can be used for tomatoes and peach packed in PLA-based EMAP
controlling the in-package RH. In this way, the in-package atmo-
sphere can be adjusted to the required composition with respect to The analytical model of Mistriotis and Briassoulis (2012) was
all relevant gases that are important for a specific horticultural pro- used and computer-simulations were carried out (Briassoulis et al.,
duce. Since the O2 permeability of such materials is similar to CO2 , 2012) to design the optimum 200 m micro-perforation pat-
oxygen concentration can also be efficiently regulated through the tern and calculate the area of the 30 m PLA film needed for
perforation together with CO2 concentration. the packaging of fresh cherry tomatoes and peach fruit. This
investigation involved modelling, analysis and determination of
2.3. Bio-based packaging materials permeability characteristics of the EMAP system that achieves
micro-environmental dynamic conditions meeting the design
PLA film was selected among other bio-based films as the EMA requirements of fresh cherry tomatoes and peach fruit described
packaging material for several reasons: PLA (Poly(lactic acid) is the in Table 1.
first polymer based on renewable raw materials commercialized at The performance of so developed novel EMAP system on
a large scale; it is a compostable material, meeting the specifica- postharvest decay incidence and overall quality of cherry toma-
tions of international standards (CEN, 2005). PLA is stable within toes and peaches was evaluated through a first series of full-scale
the functional life time of a package for fruits and vegetables; its experiments conducted under refrigeration storage conditions
D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80 71
Table 2
Mechanical properties of the PLA films of nominal thicknesses 30 m and 20 m in parallel direction.
Tested samples in the parallel direction Thickness (mm) Tensile strength (MPa) Elongation at break (%)
PLA film of nominal thickness 30 m 0.028 0.0010 57.02 2.48 6.88 1.16
PLA film of nominal thickness 20 m 0.018 0.0007 65.68 3.16 7.32 1.67
followed by ambient shelf conditions with peach cultivars mechanical properties are concerned, the 20 m film can be used
(‘Rich Lady’, ‘Dixired’) and cherry tomato cultivars ‘Creative’, Fra- for the EMAP system instead of 30 m PLA film, provided that it
garia × ananassa cv. Candonga (D’Aquino et al., 2011a, 2012a,b). can also be handled without problem by the packaging machines.
Overall results showed a better performance of PLA with respect The WV permeance of a 20 m PLA film was measured equal to
to OPP in maintaining quality and in reducing decay for both peach 0.085 × 10−5 g m−2 s−1 Pa−1 (sample thickness 17 m). This value
cultivars under simulated market condition. In the case of cherry is about 1.5 times higher than the measured permeance of a 30 m
tomatoes, RH in OPP bags was 94–97%, leading to a higher per- PLA film which was found equal to 0.061 × 10−5 g m−2 s−1 Pa−1
centage of decay (D’Aquino et al., 2011a). The effect of PLA bags on (sample thickness 27 m). The mechanical and barrier properties
cherry tomatoes quality was similar to OPP bags, both regarding of the 20 m PLA film indicate its potential suitability as a cost
chemical parameters and market quality (weight loss, appearance, efficient EMAP solution for packaging of fresh fruits and vegetables.
and firmness) (D’Aquino et al., 2012a).
3.1.1.2. Processing of micro-perforation of 20 m PLA films. The tests
3. Overall evaluation and design optimization of novel PLA performed at Mach s.r.l. (Obetti, 2012; ‘HortiBioPack’, 2008) showed
EMAP system that laser micro-perforation of a very thin 20 m PLA film results
in damages of the film at additional spots, with the formation of
3.1. Optimization of EMAP design in terms of bio-based material unexpected, unpredictable and uncontrolled openings. The occur-
rence of unwanted and unpredictable holes in a 20 m thick film
The novel EMAP design has been shown through the first series demonstrates that such a thin PLA film is not suitable for industrial
of full-scale experiments under refrigeration and market storage laser micro-perforation processing. It was concluded that a PLA film
conditions for selected cultivars of peach and cherry tomatoes to with 30 m thickness has an optimum balance between material
be optimum for 30 m PLA film in terms of film processing and cost and performance in terms of headspace atmosphere achieved
micro-perforation (D’Aquino et al., 2012b). However, as the film by the optimal micro-perforation process following the developed
area is controlled by the targeted headspace RH (Mistriotis and EMAP design.
Briassoulis, 2012; Briassoulis et al., 2012), the so designed EMAP Nevertheless, the use of 20 m PLA film is still possible through a
may need larger film area as compared to the geometrical needs combination of strips of micro-perforated 30 m PLA films bonded
of a given volume of the packed produce, depending on the WV to non-perforated 20 m PLA film covering at least half of the
control requirements. This may result in a higher cost and waste of needed EMAP area (e.g. PLA 30:20 m: 50–50%) with a clear
bio-based packaging material. The optimization of the EMAP design cost/material reduction of the so produced EMA packaging bags.
with respect to bio-based material and cost was investigated along
two directions:
3.1.2. Alternative innovative solutions of bio-based EMAP design
Alternative innovative solutions of EMAP design were inves-
3.1.1. Using thinner PLA film
tigated by combining two different bio-based biodegradable
The possibility to use thinner PLA film was investigated by
packaging films integrated in the HortiBioPack EMAP design.
designing and testing an EMAP system with 20 m PLA film. The
The two materials selected were 30 m PLA film, for which
possible use of 20 m PLA film instead of 30 m PLA film has two
200 m micro-perforation has been optimized, and non-perforated
advantages:
Mater-Bi film (average thickness 38 m) which has higher WV
permeability than PLA. ‘Mater-Bi’ is a family of completely
1. It results in lower financial and environmental cost as only 2/3
biodegradable and compostable materials produced by Novamont
of PLA material of the 30 m film based EMAP is needed.
S.p.A. based on renewable raw materials (such as starches from
2. The 20 m PLA film has higher WV permeance as compared to
different crops and vegetable oils) that are complexed with
30 m PLA film. Thus a smaller film area is needed for achieving
biodegradable synthetic polyesters. Mater-Bi biodegrades com-
the targeted HR values and so packages of smaller size can be
pletely in composting, soil, fresh and salt water and is considered
used fitting better to the packed produce volume (saving mate-
to be a compostable material without ecotoxicity according to the
rial further and reducing cost).
European standard CEN EN13432 (CEN, 2005). The design approach
for the combined bio-based EMAP of cherry tomatoes is described
The questions rose with regard to the possible use of 20 m below:
PLA film with the developed EMAP design concern the mechanical
performance of the thin film when processed with the packaging
machines, the WV permeability and the success of the micro- 3.1.2.1. Theory and calculations. Based on Fick’s Law of diffusion:
perforation processing, optimized by Mach s.r.l. specifically for the
CWV
case of 30 m PLA film with 200 m micro-perforations (Obetti, JWV = Pm A (1)
2012). x
where JWV (g/s) is the water vapour mass flux; Pm (g/ms) is the
3.1.1.1. Performance of 20 m PLA films. Samples of 20 m and permeability of packaging material in terms of mass fractions; A
30 m PLA film provided by Huhtamäki Oyj, grade BIO-WARE (m2 ) is the packaging film area; CWV is the water vapour mass
were tested at the AUA laboratory. The mechanical properties of fraction difference between environment and package headspace;
these samples, shown in Table 2, confirm that, as far as their and x (m) is the packaging film thickness.
72 D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80
For a combination of two different packaging materials The areas A1 and A2 for each EMAP design were calculated in a way
as to achieve the targeted RH in-package regulation.
CWV
JWV = (Pm1 A1 + Pm2 A2 ) (2) Targeted headspace CO2 and O2 : The CO2 and O2 regulation is
x
achieved through the design of proper micro-perforations on the
A1 + A2 ≥ Atotal (3) PLA film for which the micro-perforation technique was optimized,
since both PLA and Mater-Bi films are practically impermeable to
where Pmi (g/ms) is the permeability of packaging material i; Ai CO2 . Using Eq. (4) the number and the geometrical characteristics
(m2 ) is the area of packaging film i; and Atotal is the minimum area of the micro-perforations were calculated in order to reach the tar-
of packaging film which can wrap the required produce quantity geted CO2 and O2 values of the head-space (the same as with pure
volume. PLA based EMAP; not affected by the presence of the barrier to CO2
From these equations areas A1 and A2 can be defined since: and O2 Mater-Bi film).
3.1.2.2. Modelling. An optimized EMAP using a combination of PLA 4. Experimental investigation of overall performance of
and Mater-Bi films was modelled for the case of cherry tomatoes. innovative EMAP
The data used with the Mater-Bi–PLA EMAP film combination are
as follows: 4.1. EMAP materials and design
Jwv = 5 g/day (transpiration; Table 1) The bio-based biodegradable film used in the laboratory exper-
JCO2 = 12 ml/h (or 0.14 g/day) (respiration; Table 1) iments was a 30 m BoPLA film, from Taghleef Industries L.L.C,
DCO2 in air = 1.4 × 10−5 m2 /s grade NativiaTM NTSS30 (Nativia, 2011). It is a highly trans-
PPLA = 4.66 × 10−5 (g/ms) parent film with both sides heat sealable, biodegradable &
PMater-Bi = 3 or 4 times PPLA (this variation of measured PMater-Bi led compostable. It is certified EN 13432 (2005) for compostable
to the design of two types of EMA packages for cherry tomatoes) intermediates. The barrier properties of the NativiaTM NTSS30
x = 30 film are as follows (Nativia, 2011): Water vapour perme-
RHheadspace = 80–90% (targeted value; Table 1) ability, measured according to ASTMF1249 (38 ◦ C, 90%RH), is
RHenvironment = 60–65% (storage value; Table 1) 270 g/m2 /d (1.57 × 10−11 g m−1 s−1 Pa−1 ); Oxygen permeability,
CWV calculated by the theory measured according ASTMD3985 (23 ◦ C, 0%RH), is 730 cm3 /m2 /d
CCO2-headspace = 3–5% (targeted value; Table 1) (1.25 × 10−17 m2 s−1 Pa−1 ). Micro-perforations were performed on
CCO2-environment = 0 (storage value; Table 1) the PLA film by Mach s.r.l. according to the bio-based EMAP Hort-
iBioPack design (Mistriotis and Briassoulis, 2012). Conventional
3.1.2.3. Design. Following the above modelling, the design of the macro-perforated 30 m BOPP film prepared by Mach s.r.l. was
EMAP system using the selected PLA and Mater-Bi films for cherry used for the reference EMAP bags.
tomatoes was based on three requirements: Two sets of PLA-based EMA Packages were modelled analytically
Geometric constraint: For an EMA Package containing a specific containing 250 g of cherry tomatoes and 1000 g of peaches, respec-
quantity of produce of a given average dimension (e.g. 250 g of tively. Based on the analytical model results for cherry tomatoes the
cherry tomatoes; refer to next section), a minimum needed pack- targeted range of RH values can be achieved by using a PLA packag-
aging film area Atotal is calculated (for 250 g of cherry tomatoes ing film area between 500 and 900 cm2 , while 5 micro-perforations
Atotal = 400 cm2 ). For a combination of two packaging materials of 200 m diameter are needed to control the targeted CO2 and O2
(PLA/Mater-Bi) the total film area should satisfy the constraint: concentrations (Table 1). For the peaches the required PLA pack-
aging film area was calculated to be between 1250 and 2150 cm2
A1 + A2 ≥ Atotal = 0.04 (m2 ) (5)
while 100 micro-perforations of 200 m diameter are needed to
Targeted headspace RH: Based on two different WV permeabil- control CO2 and O2 concentrations. Based on these data PLA EMAP
ities obtained through lab measurements for thin Mater-Bi films bags of 615 and 1500 cm2 for cherry tomatoes and peach respec-
and on Eqs. (2) and (5), two different EMA packages were designed. tively, were prepared for laboratory experiments and were also
D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80 73
Fig. 1. Composite bio-based EMAP system made of micro-perforated PLA film (1/2) and Mater-Bi film (1/2) (left) and micro-perforated PLA film (2/3) and Mater-Bi film (1/3)
(right).
modelled numerically (Briassoulis et al., 2012). In addition, conven- RH 65%. A series of experiments were conducted with peach variety
tional OPP EMAP packages were prepared with 4 holes of diameter Prunus persica (late production; September) delivered directly from
6 mm for the peaches and 12 holes of diameter 8 mm for the cherry farm. Each PLA and OPP EMAP bag contained three peaches (approx.
tomatoes. An additional set of PLA EMAP with reduced number of 1000 g) (Fig. 3). Six repetitions were tested with PLA EMAP and five
perforations (3× 200 m), aimed at higher CO2 concentration was repetitions with OPP EMAP, while four non-packed sets were used
also tested with cherry tomatoes. as control.
Two series of experiments were conducted with cherry toma-
4.2. Combined PLA and Mater-Bi bio-based EMAP for cherry toes: (a) cherry tomatoes Ornella, the earliest production variety,
tomatoes were collected and transported directly from Ierapetra, Crete
on 13/3/2012; (b) cherry tomatoes Genio, the smallest variety,
Two alternative optimized bio-based EMAP bag designs, based were collected and transported directly from Timpaki, Crete on
on combined PLA/Mater-Bi films, were developed at the laboratory 29/3/2012. Each PLA, PLA/MB and OPP EMAP bag contained 250 g
of AUA, specifically for cherry tomatoes. The required PLA (A1 ) and cherry tomatoes. For each cultivar, three repetitions were tested
Mater-Bi (A2 ) film areas were calculated according to the design with PLA, three with PLA-MB and three repetitions with OPP
approach described in the previous section (Atotal satisfies Eq. (5)) while two non-packed sets were used as control in each case
as follows: (Figs. 4 and 5). In addition, a set of three PLA EMAP bags with
Case I: PLA-MB EMA Package-I for 250 g of cherry tomatoes with reduced number of microholes (3× 200 m microholes) were
5 micro-perforations of 200 m diameter applied on the PLA 30 m included specifically in the experimental series of Genio cherry
film assuming that PMater-Bi = 3 PPLA :
Fig. 3. PLA based EMAP bags (left) and BOPP EMAP bags (right) used to pack 1 kg peaches.
Fig. 4. PLA based micro-perforated EMAP 12 cm × 26 cm bag (top left) with 5–200 m holes (top right); conventional macro-perforated BOPP EMAP 26 cm × 15 cm with
12–8 mm holes (bottom).
tomatoes, aimed to investigate the effect of increased CO2 concen- Mechanical properties: An INSTRON testing machine Model 4204
tration in the headspace. was used for measuring the tensile properties of EMAP films accord-
ing to the standard EN ISO 527-3.
4.3.2. Measurements Water vapour permeation of PLA film: The determination of the
4.3.2.1. Headspace conditions. Every day each bag was weighed water vapour transmission of 30 m PLA and 38 m Mater-Bi films
on a sensitive balance Ohaus Ts4kd Precision Standard (accuracy was carried out through the ASTM E96M-05 standard technique. In
±0.02 g). From the gravimetrical measurements the weight loss of the case of the tested films, the Water Method was selected that bet-
the produce and the in-package RH were calculated. The CO2 and ter approaches the conditions under consideration. Measurements
O2 in-package concentration in equilibrium was measured with were performed under 5, 10, 15, 20 and 25 ◦ C and RH 50% and 75%.
a QUBIT S147 Rapid Response O2 /CO2 Analyzer device. In addi- The water vapour weight loss was measured by an electronic Ohaus
tion each bag was visually inspected for signs of decay or other Explorer E02140 balance (precision ± 0.01 g).
phenomena related to the shelf life time and quality of the packed Optical properties: The optical properties of the tested films were
fruits. measured by using a UV/VIS/nrIR spectrophotometer (HITACHI U-
4001) with an integrating sphere.
4.3.2.2. PLA EMAP films. Following the end of the storage period Chemical composition: The possible chemical changes in the
samples of the PLA EMAP films were tested at the laboratory for polymeric structure of the tested samples were investigated after
possible changes in the following properties: the end of experimental procedures by running mid infrared
D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80 75
Fig. 5. Non-packed sets of 250 g Ornella (left) and Genio (right) cherry tomatoes.
spectra on a FTIR spectrometer (Tensor 27, Bruker Optics), either in Peach stored under 20oC and 65%
the transmission mode, or by single reflection diamond ATR spec- 110.00
troscopy.
105.00
5. Results
85.00
Table 3
Numerical simulation and laboratory experiments results for in-package gas mixture concentrations compared to the analytical model predictions.
Fruit: 250 g Ornella cherry tomatoes Film PLA 30 m CO2 : 4.0 ± 0.1a CO2 : 5.1 ± 0.3 CO2 : 5.0
Packaging material area: 615 cm2 Perforations: 5 of diameter 200 ma RH: 86 RH: 88 ± 3 RH: 86
Fruit: 1000 g peaches Film PLA 30 m CO2 : 3.3 ± 0.01 CO2 : 3.4 ± 0.2 CO2 : 3.0
Packaging material area: 1500 cm2 Perforations: 100 of diameter 200 m RH: 90 RH: 85 ± 4 RH: 86
a
Experimental CO2 result for PLA based EMAP with 3–200 m perofrations was 6.5 kPa.
deformations after two weeks of storage (15 and 13 days for Ornella
and Genio cherry tomatoes, respectively) (Fig. 9). As this two weeks
storage period is associated with 8% water loss for the Ornella
cherry tomatoes and 10% for the Genio cherry tomatoes, the 8%
and 10% water loss limits are considered as the thresholds for
defining the shelf life enhancement of the PLA-based EMAP for the
two varieties, respectively, as compared to no packaging. Based on
these threshold values, the new PLA based EMAP systems, on the
average, result in an increase of shelf-life time by 10 days (meet-
ing the 8% and 10% water loss threshold values after a storage
period of 25 and 22 days for the Ornella and Genio cherry tomatoes,
respectively). The conventional macro-perforated BOPP packaging
systems resulted in rates of water loss comparable or slightly lower
than those of PLA EMAP systems (meeting the 8% and 10% water
loss threshold values after a storage period of 21 and 17 days for the
Ornella and Genio cherry tomatoes, respectively; Fig. 8). All conven-
tional macro-perforated BOPP packaging systems exhibited signs
of shrinkage deformation, especially those located near the macro-
perforations, after approximately 16 and 21 days of storage for the
Ornella and Genio cherry tomatoes, respectively (Fig. 9). Combined
PLA/Mater-Bi based EMAP systems exhibited water loss behaviour
analogous to that of the PLA EMAP systems. No shrinkage deforma-
tion signs were detectable in the cases of cherry tomatoes packed
in PLA-EMAP and PLA/Mater-Bi EMAP.
5.3.1. Peach
The shelf life-time characteristics of the PLA-based EMAP solu-
tions for fresh peach fruits as compared to non-packed peach and
to peach packed in conventional BOPP EMAP bags are shown in
Fig. 10, expressed in terms of the average time when the first fruit
was infected in each bag of each EMAP system and the non-packed
fruits. It is clear that the PLA-based EMAP systems offer a mini-
mum shelf life-time at least the same as the one of the conventional
BOPP EMAP system. The fact, however, that BOPP EMAP is associ-
ated with the development of water vapour condensation already
from the first days of storage has a negative impact in its market
value-appearance and promotes more rapid development of var-
ious infections. On the other hand the non-packed peach fruits
present a better shelf-life in terms of fungi infection. However,
Fig. 8. Loss of water of Ornella (a) and Genio (b) cherry tomatoes packed in the new
PLA-EMAP system, PLA – Mater-Bi EMAP systems, conventional BOPP EMAP systems
these fruits loose very fast weight (water) which is also associated
and non-packed tomatoes, under 20 ◦ C – RH 65%. with degradation of their quality and their market value. It may be
concluded therefore that the PLA based EMAP system results in an
increase of shelf-life time by 12 days assuming as threshold value
the significant loss of weight and the associated quality degrada-
the loss of 8% water.
tion of the non-packed peaches (analogous results are reported by
D’Aquino et al. (2011a) for different peach cultivar).
The performance of the bio-based EMAP systems in terms of 5.3.2. Cherry tomatoes
fruit water retention for Ornella and Genio cherry tomatoes is The shelf life-time characteristics of the various PLA-based
shown in Fig. 8 against the corresponding behaviour for non-packed EMAP solutions for the Ornella and Genio cherry tomatoes as
cherry tomatoes and tomatoes packed in conventional BOPP EMAP compared to non-packed tomatoes and to tomatoes packed in con-
systems. The PLA based EMAP was shown to retain the targeted ventional BOPP EMAP bags are shown in Fig. 11 expressed in terms
RH at the level of 86%, thus preventing a fast loss of water. On of the average time when the first tomato was infected in each
the other hand, the non-packed cherry tomatoes exhibited faster bag of each EMAP system. It is clear that the PLA-based EMAP sys-
loss of water with the appearance of shrinkage related wrinkles tems offer a minimum shelf life-time comparable to, or longer than,
D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80 77
Fig. 9. Loss of water of Cherry tomatoes Ornella under 20 ◦ C – RH 65%: Signs of shrinkage deformation appear after 13 days of storage without packaging (top); Shrinkage
deformation with conventional BOPP EMAP after 29 days of storage (bottom).
that of the conventional BOPP EMAP system. The PLA-based EMAP (approx. two weeks) that affect directly their quality and their mar-
systems offer a minimum shelf life-time shorter than that of the ket value.
non-packaed Ornella tomatoes and comparable to the non-packed In general it is shown that the key factor for the commercial
Genio tomatoes. The BOPP EMAP system however, is associated deterioration of the cherry tomatoes in a time-frame of 1 month
with the development of shrinkage deformation signs in the Ornella is the weight loss rather than the fungal decay. PLA based EMAP is
and Genio cherry tomatoes located near the macro-perforations shown to retain an average shelf time of 2 months without decay
after two and three weeks of storage respectively, with a neg- (the weight loss after 2 months of storage is 20% and 25% for the
ative impact in their market value. The non-packed Ornella and Ornella and the Genio cherry tomatoes, respectivley). The optimized
Genio cherry tomatoes loose very fast weight (water) which is also PLA-Mater-Bi design was found to perform well for at least 1 month
associated with early development of shrinkage defomration signs with the observation of a few early infections that are considered
however to be irrelevant to the EMAP design. No shrinkage signs
were observed.
It is interesting to notice that the use of PLA based EMAP with
higher headspace CO2 concentration (Table 3) through the reduc-
tion of the number of microholes from 5 to 3 resulted in enhanced
shelf-life time in the case of Genio cherry tomatoes where it was
tested (Fig. 11; attributed to the micro-organisms inhibition effect
of the higher CO2 concentration).
Fig. 13. Transmission spectra of NativiaTM PLA packaging film before and after the
exposure to peach (19 days); non-exposed film (red spectrum) exposed film (blue
spectrum).
Height (%)
8 8,0
6 6,0 1 month
19 days storage
4 storage 4,0
2,0
2
0,0
0 350 45 0 550 65 0 750
350 450 550 650 750
Wavelength (nm)
Wavelength (nm)
Fig. 12. Haze (%) of the NativiaTM PLA packaging film tested through UV-Vis spectrometry before and after the exposure to peach (19 days) (a) and cherry tomatoes (1 month)
(b).
D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80 79
Fig. 14. DSC thermographs of NativiaTM PLA packaging film before and after the exposure to peach (19 days); non-exposed film (a) exposed film (b); note: Tg = glass transition
temperature (∼59 ◦ C), crystallization point ∼ 119 ◦ C, melting point ∼ 150 ◦ C.
mechanical properties of EMAP films used for 1 month with cherry simulations. Comparisons with non-packed commodities and com-
tomatoes, no further testes were carried out for this film. modities packed with conventional oriented polypropylene (OPP)
show improved shelf-life time of peach and cherry tomatoes packed
in the PLA and PLA/Mater-Bi based EMAP systems. Results on decay
6. Conclusions control confirmed earlier published results on the positive effect
of the PLA EMAP of peach and cherry tomatoes in improving the
An innovative biodegradable bio-based equilibrium modified quality characteristics and controlling better fungal decay of these
atmosphere packaging (EMAP) of high value fresh horticultural fruits, as compared to conventional BOPP EMAP systems. The expo-
produce has been developed through optimized design of bar- sure of the PLA film to the EMA packed fresh produce conditions
rier properties combining laser micro-perforation and breathable during the shelf-life period has negligible effect on the mechanical,
membrane technologies and materials. Laboratory experiments physical and chemical properties of the film.
with EMAP of fresh peach and cherry tomatoes under shelf con- The novel PLA-based EMAP system based on the presented opti-
ditions were employed in order to validate the analytical model mized design and evaluated experimentally is shown to be stable
and the 3D numerical simulations used for the optimal design of and efficient for packaging of fresh horticultural produce.
the innovative EMAP system. Laser micro-perforated 30 m poly-
lactic acid (PLA) film was used as packaging material. An EMAP
system based on a combination of micro-perforated PLA and non- Acknowledgements
perforated Mater-Bi films aimed at the material optimization was
also designed and tested. Conventional macro-perforated 30 m This research was supported by the European FP7 project:
BOPP film was used as a reference EMAP systems and non-packed “Development of innovative biodegradable packaging system to
fruits were used as control. improve shelf life, quality and safety of high-value sensitive hor-
Results from the lab experiments were found to be in agreement ticultural fresh produce” (FP7-SME-2008-1-232551-HortiBioPack).
with the predictions of the analytical model and the numerical Thanks are due to Ms. E.Babou for testing the film properties.
80 D. Briassoulis et al. / Industrial Crops and Products 48 (2013) 68–80