ANALYTICAL METHOD FOR THE DETERMINATION OF THE

AROMA PERMEATION THROUGH PACKAGING MATERIALS

Eric MARTINE, Packaging Laboratory, School of Business and Engineering Vaud (HEIG-VD),
1401 Yverdon-les-Bains, Switzerland, eric.martine@heig-vd.ch
Didier LOUVIER, Packaging Laboratory, School of Business and Engineering Vaud
(HEIG-VD), 1401 Yverdon-les-Bains, Switzerland

ABSTRACT. One of the roles of a packaging material is to preserve the aromas of the packed product.
In order to choose the right material to preserve the aroma, it would be interesting to have the possibility
to determine the aroma permeation. To date numerous studies were realized concerning the permeation
(or the mass transfer) of an aroma through a synthetic packaging material including the methods of
analysis (dynamic or static (manual taking)).
The purpose of the present study is to develop an automated and easy to operate analytical method
based on an autosampler static headspace feeding a chromatograph with gaseous phase coupled with
the mass spectrometer detector (HS-GC-MS) for the determination of the diffusion and permeability
coefficients for a couple aroma / synthetic material.
To automate this method, a module of automatic piloting and a measure cell conceived from an existing
vial were developed.
For the validation of the analytical method, the couples composed of an aroma such as limonene,
menthone and hexane and a synthetic material such as LDPE, OPP, OPET, OPA, PLA and metallised-
PLA were studied. The results got by this method are compared with these one of the gravimetric
method and the dynamic method GC-MS by electronic impact.
So, the automated method static HS-GC-MS coupled with a module of automatic piloting is adapted for
aroma / synthetic material couples presenting a high permeability coefficient.

KEYWORDS. Aroma; diffusion coefficient; permeability coefficient; HS-GC-MS; permeation; permeation

cell

INTRODUCTION
An aroma is a chemical substance sensed by the taste and / or the smell defined by
parameters such as its volatility, its polarity, its aromatic value ... [1, 2]
The aromas must be protected throughout the retail chain until its use. The conservation of
these aromatic contents is mainly based on the packaging where the aroma / packaging
couple can be confronted with the appearance of off-flavor in the packaging, the total or
selective loss of aromas. Behind this difficulty, several well known phenomena are hidden
such as the scalping, the permeation (or mass transfer), the porosity and the migration, but in
general not easily quantifiable [3].

At present, the literature deals mainly with the understanding of the phenomena of mass
transfer through synthetic materials and few about the quantification of their aroma
permeation.

The offer, both in method and in equipment, is weak; the methods being complex, long to
implement and demand specific and not automated installations. The current methods for the
determination of the aroma permeation are dynamic test cell and static test cell [4, 5, 6, 7, 8].

The present study proposes to develop and assess a method for the determination of the
aroma permeation based on the static method HS-GC-MS composed of:
• the realization of a simple permeation cell, cheap and easy to implement,
• the development of an automated static analytical method compared with a dynamic
method GC-MS by electronic impact and with a gravimetric method.

Copyright 2010 © LEC Page : 1 / 8

HEIG-VD / LEC Date : 10/12/2010

MATERIALS AND METHODS

Aroma
3 aromas are used in the study namely: R-(+)-limonene, ref. Fluka 62120, hexane, ref. Fluka
52770 and menthone, ref. Firmenich 00176.

Synthetic materials for packaging

All materials tested in this study provide from the field of packaging: LDPE, low density
polyethylene, thickness e = 155μm, Früh Verpackungs-Technik AG; OPP, biaxially oriented
polypropylene, e = 50μm and OPA, polyamid, e = 50μm Elag Verpackungen; PLA and
metallised-PLA, polylactide acid, respectively e = 40μm and = 30μm, Polyfilms; OPET,
polyester type Mylar, e = 23μm, Dupont de Nemours.

Methods
HS-GC-MS analytical method
Permeation cell (cf. picture 1)
The permeation cell in aluminum, developed in this study, is realized on the basis of the
dimensions of a standard glass vial (Milian, ref. LPP 20090297, 20mL flask headspace 75.5 x
23mm). It consists of 2 half-chambers screwed together and compatible with the auto-sampler
HS. A membrane of 17mm-diameter (surface of exchange ≈ 2,27cm2), taken from materials
by a punch is put down in the upper ½-chamber of the permeation cell. Immediately after the
introduction of the aroma, the upper and lower chambers are screwed and the upper ½-
chamber closed with a cap and a septum (Milian, ref. LPP 20030142, ultraclean 20 mm
aluminium cap, blue transparent silicone / white PTFE).

Relative humidity in permeation cell (cf. picture 2)

Some measures can be realized by modifying the relative humidity in the lower ½-chamber. A
saturated solution of salt in distilled water (5 mL), in function of the relative humidity, and a
crucible containing the testing aroma (100 μL) are introduced into the lower ½-chamber.
Immediately after the introduction of the crucible, a membrane of 17mm-diameter is put down
in the upper ½-chamber of the permeation cell and the ½-chambers are screwed. The upper
½-chamber is closed with a cap and a septum.

Picture 1. Permeation cell Picture 2. Permeation cell and relative humidity

HS-GC-MS method
The permeation cell is introduced into the auto-sampler HS. The gaseous phase of the
headspace from the upper ½-chamber of the permeation cell is taken by the needle of the
auto-sampler HS and injected in a chromatograph in gaseous phase (GC) coupled with a
mass spectrometer (MS).

The injections, defined in function of the aroma / synthetic material couple, are realized at
regular intervals up to the steady rate of the permeation is reached (cf. graph 1).
To pilot automatically the HS and then the analytical chain, a module of piloting is developed.
The first trials for the validation of the analytical chain: module of piloting / permeation cell /
HS-GC-MS lead to hold the following method (cf. table 1):

Copyright 2010 © LEC Page : 2 / 8

HEIG-VD / LEC Date : 10/12/2010

Apparatus References Parameters

Static headspace HS 40XL, 40 positions, Thermostatisation (HS oven): 1 min at 45°CÚ1

2
auto-sampler (HS) Perkin Elmer InjectionÚ : depend on the aroma
Gas Chromatograph Auto System XL, Perkin
Oven temperature: 80°C / Injector: CAP: 150°C
(GC) Elmer
Fused silica, crosslinked methyl siloxane 25m x i.d.
Column HP-1MS, Supelco 0,2mm x 0,3μm film thickness
Carrier gas: Helium 70kPa, 25cm/s
Interface temperature: 180°C, source temperature:
Mass spectrometer Turbomass, Perkin 160°C
(MS) Elmer
FULL scan and SIR (m/z depend on the aroma)
Table 1. Apparatus
Ú1
: HS oven temperature limited by the HS technique, permeation cell introduced into less than 2min.
Ú2
: The injection time is function of the aroma: limonene and menthone = 0.05 min, hexane = 0.02 min.

To define the HS-GC-MS method, the following parameters were determined for the 3
aromas: linearity, limits of detection (LOD) & quantification (LOQ). For the LOD (S/N=3) and
LOQ (S/N=10), respectively in SIR mode for limonene equal to 0.01ppm and 0.04ppm, for
menthone <1ppm and <4ppm and in full mode for hexane <40ppm and <140ppm.

Gravimetric method
For the determination of the aroma permeation by gravimetric method, the preparation of the
permeation cell is realized according to the same protocol as for the HS-GC-MS method but
the cell is left opened to the ambient air. The permeability profile is realized by weighing the
permeation cell at regular intervals with a scale having a sensibility of ± 0.1mg. For the
measures realized at a relative humidity different from 50%, the permeation cell is maintained,
during all the test period into a climatic cabinet containing the relative humidity of test.

GC-MS method by electronic impact

This method is used by a research partner to compare their results with the HS-GC-MS
method results. GC-MS EI is a dynamic method using a chromatograph in gaseous phase
coupled with a mass spectrometer. A permeation cell composed of 2 ½-chambers is directly
introduced into the GC oven.

Copyright 2010 © LEC Page : 3 / 8

HEIG-VD / LEC Date : 10/12/2010

RESULTS & DISCUSSION

Permeability profile by HS-GC-MS
The graph 1 shows a permeability profile obtained for the limonene / LDPE couple by the HS-
GC-MS method. The phase I allow to determine the diffusion coefficient (D) and the phase
II the permeability coefficient (P).

Mass of limonene = f (time)

Limonene 50uL / LDPE 155um
Mass of lim onene at 23°C
[m g]

0.16
Phase I Phase II
0.14

0.12

0.10

0.08
D1/2 = 7,35.10-9 cm2/s P = 35 g.μm/m2.d.Pa
0.06

0.04

0.02

0.00
0 50 100 150 200 250 300 350
Tim e [m in]

Graph 1. Permeability profile by HS-GC-MS method

Permeability profile by gravimetric method

The graphs 2 and 3 show the loss respectively of the limonene through a LDPE membrane
and the limonene through an OPA membrane.

Aroma loss = f(time)

LDPE / Limonene
at 23°C / 50% r.h.

0.00
0 2 4 6 8 10 12 14 16 18 20
-10.00

-20.00

-30.00 P0.04 th -8 th = 26 g.μm/m2.d.Pa

-40.00

-50.00

-60.00

-70.00

-80.00

Time [day]

Graph 2. Permeability profile by gravimetric method - Limonene / LDPE couple

From the graph 2, it is possible to determine P for the limonene / LDPE couple. In this
example, the coefficient is determined between the 0.04th (1 hour) and the 8th day.

Copyright 2010 © LEC Page : 4 / 8

 HEIG-VD / LEC Date : 10/12/2010

Aroma loss = f(time)

OPA [50um] / Limonene
1
at 45°C / 55%h.r.

0.00
0 5 10 15 20 25 30 35 40 45
-0.50

-1.00

-1.50

-2.00 st th -2 2
P1 -28 = 2,3.10g.μm/m .d.Pa
-2.50

-3.00
Time [day]

1
: relative humidity mean for the test

Graph 3. Permeability profile by gravimetric method - Limonene / OPA couple

At the view of the first analyses at 23°C for the limonene / OPA couple (no important mass
transfer after 139 days), the temperature test was increased to be able to obtain a transfer in
a reasonable time without better result (cf. graph 3 at 45°C). The OPA seems to be a good
barrier to the limonene.

Diffusion and permeability coefficients

For different aroma / synthetic materials couples, the results of the D and P obtained by the
HS-GC-MS and gravimetric methods are compared to the literature (cf. table 4).

Diffusion coefficient D1/2 [cm2/s] Permeability coefficient P [g.μm / m2.d.Pa]

Couples Measured [23°C / 50% r.h.]
HS-GC-MS Literature [23°C] Literature [23°C]
HS-GC-MS Gravimetry
20Ú1
-9 4,6.10-10 to 26 9 → 124 [20°C /
14 → 35Ú (n=7)
LDPE / limonene 7,03.10 2
4,3.10-9 Ú3 26 → 27 (n=3) 65% r.h.]

-8 -8 47 3,11
LDPE / hexane 3,81.10 25°C, 1,05.10 1.38
34 → 59 (n=3) 3,09 → 3,15 (n=3)

LDPE / 5
1,97.10-9 2,1.10-9 N.A. Ú4 N.A.
menthone 4 → 5 (n=3)

-9 -9 10 8
9.10 → 0.6
-2
OPP / limonene 1,17.10 25°C, 0,65.10
2 → 14 (n=3) 7 → 8 (n=6)
17 1,09
OPP / hexane 6,71.10-9 N.A. N.A.
10 → 22 (n=3) 0,41 → 2,02 (n=3)
-11
OPP / menthone 5,45.10 N.A. 3 N.A. N.A.
Table 4. Diffusion and permeability coefficients
Ú1 2 3 4
: Average of P / Ú : Interval of P / Ú : Number of D and P / Ú : N.A. = No Available

Copyright 2010 © LEC Page : 5 / 8

HEIG-VD / LEC Date : 10/12/2010

For the others materials, we get the following P [g.μm / m2.d.Pa] by gravimetric method [23°C
and 50%r.h.] vs literature [23°C]:
• Limonene / OPET: 3,6.10-2 (n=3, between 6th and 40th day) vs 1,45.10-5 - 1.10-3
• Limonene / PLA: 7,1.10-2 and 0,27 at 45°C (n=3, between 6th and 40th day) vs <8,6.10-5
at 45°C
• Limonene / PLA-met: No available results (Some cracks appear in the metallised layer).
• Limonene / OPA: No mass loss after 139days at 23°C; 2,3.10-2 at 45°C (n=3, between 1st
and 28th day) vs 8,5.10-6 (6,5.10-4 at 75%r.h.)
• Hexane / OPET: No mass loss after 6 days

The results obtained by HS-GC-MS method (table 4) show that this method is well adapted
for aroma / synthetic material couples with a fast mass transfer such as LDPE / limonene.
The couples for which we obtain coherent D are LDPE / limonene, hexane and menthone and
OPP / limonene, hexane and menthone (confirmed by the table 6).
As far as P is concerned, the results are acceptable for the couples LDPE and OPP /
limonene.

In our case, for the other tested materials (OPET, OPA, PLA, met-PLA), the HS-GC-MS
method is not adapted for the determination of D and P. Some profiles can not be obtained or
demand a very long analysis time, from several weeks in certain case. Moreover, for PLA and
met-PLA with limonene some cracks appear in the materials.
Moreover the analysis equipment is not adapted to be used for a so long time for a single
analysis because of, or example, the MS sensibility is altered along the time.

For LDPE and OPP materials, P obtained by gravimetry compared to HS-GC-MS method (cf.
table 4) are comparable for limonene and show an important difference for hexane.
For the other materials, the gravimetric method confirms the need to have a long analysis
time to get results. Moreover P determined by gravimetry are in general comparable to those
found in the literature [9, 5, 10, 11, 3, 12, 13, 14, 8].

D and P for the limonene / LDPE couple in function of relative humidity

In view of the previous results, the study of the influence of the relative humidity on the mass
transfer of an aroma through a packaging material was realized for the couple limonene /
LDPE.

Method Coefficient at 23°C 20% r.h. 50% r.h. 90% r.h.

2 -9 -9 -9
Mean diffusion D [cm /s] 5,34.10 7,03.10 5,23.10
HS-GC-MS 14 (n=3) 20 (n=7) 7 (n=3)
Permeability P [g.μm / m2.d.Pa]
9 → 18 14 → 35 6→8

2 13 (n=3) 26 (n=3) 13 (n=3)

Gravimetry Mean permeability P [g.μm / m .d.Pa]
13 26 → 27 12 → 15
Table 5. Comparison of the diffusion and permeability coefficients of the HS-GC-MS and gravimetric
methods for different relative humidity for the limonene / LDPE couple

We notice that D and P (cf. table 5) are lower for 20 % and 90 % relative humidity compared
with those for a relative humidity of 50 % whatever the analytical methods used.

Copyright 2010 © LEC Page : 6 / 8

HEIG-VD / LEC Date : 10/12/2010

Comparison of the diffusion coefficients by HS-GC-MS method vs GC-MS IE method

D obtained by both analytical methods (HS-GC-MS and GS-MS EI) have a rather good
coherence (cf. graph 5) confirmed by the diffusion coefficients provided by the literature.

Diffusion coefficient for aroma / synthetic materials at 23°C

D [cm2/s]
3.50E-08

3.00E-08

2.50E-08

GC-MS EI
2.00E-08 HS-GC-MS
Hexane Literature

1.50E-08

1.00E-08
Decane

5.00E-09

Hexane
Heptane
GC-M S EI HS-GC-M S
N.D. 5.87E-11 5.45E-11
0.00E+00
Hydrocarbon Limonene Menthone Hydrocarbon Limonene Menthone

LDPE OPP
Couple aroma / synthetic materials

Graph 5. Mean diffusion coefficients coming from the HS-GC-MS, GC-MS IE methods and literature

Concerning the hydrocarbon / LDPE couple, the difference of D can be explained by the
difference of the size between the decane and the hexane.

CONCLUSION
This study shows that the ideal couple for which the determination of the permeability profile
of aromas work is LDPE and OPP / limonene i.e. for couples having a high P.
To facilitate the determination of the permeability profile for the other materials by the HS-GC-
MS method the temperature of analysis must be increased (Arrhenius’ law).

The variation between the D and P measured and given by the literature can be explained by
(cf. table 1 and graph 4):
• In our case, the membrane of the packaging material presents a weak surface of
exchange: S ≈ 2.27cm2 so involving a reduced sensibility (surface fixed by the
equipment).
• For a same aroma / material couple, the difference of D and P can result from
conditions of manufacturing and from the nature of the material to know the
cristallinity, the percentage of bi-orientation, the presence of additives ...
• Swelling phenomena. For example, 1st value given for the limonene and 2nd for the
hexane: LDPE thickness increases about +6% and +2%, OPP +2% and +5%, PLA
+8% and +2%...

Thus, in view of the results, future studies concerning the aroma permeation should carry on:
• a better understanding of what takes place into the material at the molecular level and
in particular concerning the solubility coefficient,
• the swelling phenomenon and the influence of the relative humidity.

ACKNOWLEDGEMENTS
The authors thank:
• the University of Applied Sciences, Western Switzerland (HES-SO) as well as the
School of Business and Engineering (HEIG-VD) for their funds,
• the research partner represented by Prof. Jean-Nicolas Aebischer, College of
Engineering and Architecture of Fribourg (EIA-FR).

Copyright 2010 © LEC Page : 7 / 8

HEIG-VD / LEC Date : 10/12/2010

REFERENCES
1. J.O. Bosset, Arômes et emballages alimentaires quelques aspects analytiques, ISECA
Colloque, Station fédérale de recherches laitières, Liebefeld, Suisse, 1994
2. M.G. Sajilata, K. Savitha, R.S. Singhal, and V.R. Kanetkar, Scalping of Flavors in
Packaged Foods, Comprehensive Reviews in Food Science and Food Safety, institute of
Food Technologists, vol. 6, pp. 17-35, 2007
3. J.P.H. Linssen, R.W.G. van Willige, M. Dekker, Novel Food Packaging. Chapter 8:
Packaging-flavour interactions, pp.144-171
4. M.L. Puglisi, F. Masino, A. Antonelli, P. Fava, Study of aroma and polymer interactions,
2003
5. Q. Zhou, B. Guthrie, K.R. Cadwallader, Development of a System for Measurement of
Permeability of Aroma Compounds through Multilayer Polymer Films by Coupling
Dynamic Vapour Sorption with Purge-and-Trap/Fast Gas Chromatography, Packaging
Technology and Science, vol. 17, pp. 175-185, 2004
6. Casimir, LNE, Méthodes de mesure de la perméabilité aux arômes et aux vapeurs
organiques des matériaux polymères, Lettre de Casimir N°1, 1996
7. D. Darby, K. Cooksey, R. Kimmel, Flavor and Aroma Permeation Concepts and
Applications, 2007
8. EVAL Americas, Flavor and aroma barrier properties of EVAL® resins, Technical Bulletin
N°. 190, 2000
9. Z. Zhang, L.T. Lim, M.A. Tung, Limonene Transport and Mechanical Properties of EVOH
and Nylon 6, 6 Films as Influenced by RH, Journal of Applied Polymer Science, 79, pp.
1949-1957, 2001
10. R. Auras, B. Harte, S. Selke, An Overview of polylactides as Packaging Materials, Wiley-
VCH, Macromolecular Bioscience, vol. 4 pp. 835-864, 2004
11. M. Vähä-Nissi, T. Hjelt, M. Jokio, R. Kokkonen, J. Kukkonen and A. Mikkelson, New
Method for Aroma Barrier Testing, Packaging Technology and Science, 2007
12. R.l Auras, B. Harte and S. Selke, Sorption of ethyl acetate and d-limonene in poly(lactide)
polymers, Journal of the Science of Food and Agriculture, vol. 86, pp. 648-656, 2006
13. Otto G. Piringer, Verpackungen für Lebensmittel : Eignung, Wechselwirkungen,
Sicherheit, VCH, 1993
14. Michelle Stevens, Case study – Permeation Testing of Flavor / Aroma Compounds, 11th
International Lippke / Mocon Conference, Koblenz, Germany, September 22, 2009
15. R. Ahvenainen, Novel food packaging techniques, Woodhead Publishing Limited, 2003
16. S. C. Fayoux, A.-M. Seuvre and A. J. Voilley, Aroma Transfers in and through Plastic
Packagings: Orange Juice and d-Limonene. A Review. Part I: Orange Juice Aroma
Sorption, Packaging Technology and Science, vol. 10 pp 69-82, 1996

CONTACT
Prof. Didier Louvier, R&D Manager, Packaging Laboratory
Eric Martine, R&D Engineer, Packaging Laboratory
School of Business and Engineering Vaud, Packaging Laboratory, Route de Cheseaux, 1,
Yverdon-les-Bains CH-1401, Switzerland
Tel: +41 24 557 62 76, Fax: +41 24 557 62 77, http://lec.cett.ch, e-mail: lec@heig-vd.ch

Copyright 2010 © LEC Page : 8 / 8