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 metallisedPLA 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.

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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 = 155m, Frh Verpackungs-Technik AG; OPP, biaxially oriented polypropylene, e = 50m and OPA, polyamid, e = 50m Elag Verpackungen; PLA and metallised-PLA, polylactide acid, respectively e = 40m and = 30m, Polyfilms; OPET, polyester type Mylar, e = 23m, 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 -chamber of the permeation cell. Immediately after the introduction of the aroma, the upper and lower chambers are screwed and the upper 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 -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 L) are introduced into the lower -chamber. Immediately after the introduction of the crucible, a membrane of 17mm-diameter is put down in the upper -chamber of the permeation cell and the -chambers are screwed. The upper -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 -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):

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Apparatus Static headspace auto-sampler (HS) Gas Chromatograph (GC) Column

References HS 40XL, 40 positions, Perkin Elmer Auto System XL, Perkin Elmer HP-1MS, Supelco

Parameters Thermostatisation (HS oven): 1 min at 45C 2 Injection : depend on the aroma
1

Oven temperature: 80C / Injector: CAP: 150C Fused silica, crosslinked methyl siloxane 25m x i.d. 0,2mm x 0,3m film thickness Carrier gas: Helium 70kPa, 25cm/s Interface temperature: 180C, source temperature: 160C FULL scan and SIR (m/z depend on the aroma)

Mass spectrometer (MS)

Turbomass, Perkin Elmer

Table 1. Apparatus
1 2

: HS oven temperature limited by the HS technique, permeation cell introduced into less than 2min. : 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 -chambers is directly introduced into the GC oven.

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RESULTS & DISCUSSION Permeability profile by HS-GC-MS The graph 1 shows a permeability profile obtained for the limonene / LDPE couple by the HSGC-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 at 23C

Mass of lim onene [m g] 0.16

Phase I 0.14 0.12 0.10 0.08 D1/2 = 7,35.10-9 cm2/s 0.06 0.04 0.02 0.00 0 50 100 150 200 250

Phase II

P = 35 g.m/m2.d.Pa

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 23C / 50% r.h.

0.00 -10.00 -20.00 -30.00 -40.00 -50.00 -60.00 -70.00 -80.00 0 2 4 6 8 10 12 14 16 18 20

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

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.

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Aroma loss = f(time) OPA [50um] / Limonene at 45C / 55%h.r.

1

0.00 0 -0.50 -1.00 -1.50 -2.00

st -28 th

10

15

20

25

30

35

40

45

P1
-2.50 -3.00

= 2,3.10g.m/m .d.Pa

-2

Time [day]

: relative humidity mean for the test

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

At the view of the first analyses at 23C 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 45C). 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] Couples HS-GC-MS Literature [23C] 4,6.10-10 to 4,3.10-9
-8

Permeability coefficient P [g.m / m2.d.Pa] Measured [23C / 50% r.h.] HS-GC-MS 20 14 35

3 1 2

Literature [23C] 9 124 [20C / 65% r.h.] 1.38

Gravimetry 26

LDPE / limonene

7,03.10

-9

(n=7)

26 27 (n=3) 3,11 3,09 3,15 (n=3) N.A. 8 7 8 (n=6) 1,09 0,41 2,02 (n=3) N.A.
4

LDPE / hexane LDPE / menthone OPP / limonene

3,81.10

-8

25C, 1,05.10 2,1.10-9

47 34 59 (n=3) 5 4 5 (n=3)

1,97.10-9
-9

N.A. 9.10 0.6

-2

1,17.10

25C, 0,65.10

-9

10 2 14 (n=3) 17 10 22 (n=3) 3

OPP / hexane OPP / menthone

6,71.10-9 5,45.10
-11

N.A. N.A.

N.A. N.A.

Table 4. Diffusion and permeability coefficients

1

: Average of P /

: Interval of P /

: Number of D and P /

: N.A. = No Available

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For the others materials, we get the following P [g.m / m2.d.Pa] by gravimetric method [23C and 50%r.h.] vs literature [23C]: 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 45C (n=3, between 6th and 40th day) vs <8,6.10-5 at 45C Limonene / PLA-met: No available results (Some cracks appear in the metallised layer). Limonene / OPA: No mass loss after 139days at 23C; 2,3.10-2 at 45C (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 23C Mean diffusion D [cm /s]

2

20% r.h. 5,34.10

-9

50% r.h. 7,03.10

-9

90% r.h. 5,23.10 68 13 (n=3) 12 15

-9

HS-GC-MS

Permeability P [g.m / m2.d.Pa]

2

14 (n=3) 9 18 13 (n=3) 13

20 (n=7) 14 35 26 (n=3) 26 27

7 (n=3)

Gravimetry

Mean permeability P [g.m / m .d.Pa]

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.

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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 23C

D [cm2/s]
3.50E-08

3.00E-08

2.50E-08 GC-MS EI 2.00E-08

Hexane

HS-GC-MS Literature

1.50E-08

1.00E-08
Decane

Heptane

Hexane

5.00E-09

N.D.

GC-M S EI HS-GC-M S 5.87E-1 1 5.45E-1 1

0.00E+00 Hydrocarbon Limonene LDPE Menthone

Hydrocarbon

Limonene OPP

Menthone

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-GCMS 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).

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REFERENCES 1. J.O. Bosset, Armes et emballages alimentaires quelques aspects analytiques, ISECA Colloque, Station fdrale de recherches laitires, 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, Mthodes de mesure de la permabilit aux armes et aux vapeurs organiques des matriaux polymres, Lettre de Casimir N1, 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, WileyVCH, Macromolecular Bioscience, vol. 4 pp. 835-864, 2004 11. M. Vh-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 fr 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

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