ANALYTICAL METHODS FOR SCREENING OF POTENTIAL VOLATILE MIGRANTS FROM ACRYLIC-BASE ADHESIVES USED IN FOOD CONTACT MATERIALS Cristina Nerin, Elena Canellas, Margarita Aznar, Paul Silcock To cite this version: Cristina Nerin, Elena Canellas, Margarita Aznar, Paul Silcock. ANALYTICAL METHODS FOR SCREENING OF POTENTIAL VOLATILE MIGRANTS FROM ACRYLIC-BASE ADHESIVES USED IN FOOD CONTACT MATERIALS. Food Additives and Contaminants, 2009, 26 (12), pp.1592-1601. ฀10.1080/02652030903161572฀. ฀hal-00573888฀ HAL Id: hal-00573888 https://hal.archives-ouvertes.fr/hal-00573888 Submitted on 5 Mar 2011 HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés. Food Additives and Contaminants #! $ $ ' ( 6 * +, *1 + 0 *" / +, ' 2 3* 4 ,'+ 5 $ 7 $ " / 4 1* 9 # " ## - # (. / 0 * (. / 0 * (. / 0 * * / $ * * # $ " " / $ " $ " $ " $ $ * $ 8 6 On ## - ) w $ # 6 $ & ie " % ev rR ee rP Fo !" / * *4 ly http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk : / / Food Additives and Contaminants Page 1 of 25 1 ANALYTICAL METHODS FOR SCREENING OF POTENTIAL VOLATILE 2 MIGRANTS FROM ACRYLIC-BASE ADHESIVES USED IN FOOD CONTACT 3 MATERIALS 4 5 C.Nerín*, E.Canellas ,M.Aznar and 2P.Silcock 6 Analytical Chemistry Department, GUIA Group, I3A, CPS 7 University of Zaragoza, Mª de Luna 3, 50018 Zaragoza, Spain. 8 cnerin@unizar.es 9 2 Fo Waters Corporation, Manchester, UK 10 rP 11 Abstract 12 Two different analytical techniques, were studied for screening the volatile compounds 13 present in pure adhesives and those coming from the adhesives in different laminates. 14 Three different adhesive formulations were used for the study, all of them acrylic-based 15 and supplied by different producers. Laminates with polypropylene and paper, 16 polypropylene and polyethylene and aluminium and polyethylene as substrates were 17 prepared and studied. Adhesives themselves were acetonitrile extracted and volatiles 18 identified by time-of-flight mass spectrometry based on accurate mass measurement of 19 molecular and main fragments. The volatiles in the films themselves were determined 20 by a headspace solid phase microextraction analysis followed by GC/MS. Significant 21 differences were found within the adhesive formulations. Compounds detected in the 22 screening were assessed in terms of migration through the laminate polypropylene and 23 paper into polyethylene used as a matrix simulating food. The concentration of the 24 compounds in the polyethylene ranged from 0.04 to 1.6 µg/dm2 in the polypropylene 25 side, and from 0.27 to 28 µg/dm2 in the paper side. The most toxic compound detected 26 in the screening, 2,4,7,9-tetramethyl-5-decyne-4, was not found in any of the sides. 27 Analytical features were also calculated to provide the conditions for quantitative 28 purposes. Sensitivity was at low ng/dm2 of polyethylene and the RSD was below 10%. . iew ev rR ee ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 29 30 31 Keywords: screening, adhesives, food packaging, GC-TOF-MS, SPME, laminates, 32 analysis, migration, acrylic http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 2 of 25 Food Additives and Contaminants 33 34 Introduction 35 Most food packages and food contact materials are multilayer materials manufactured 36 using different substrates and adhesives. Although most of the substrates have to fulfil 37 the legislation for being in contact with food (Directives 2002/72 EU, 2007/19/EC for 38 plastics and Resolution AP 2002 approved by the Council of Europe for paper and 39 boards), adhesives, are not yet regulated. 40 Fo 41 The adhesive industry uses a large variety of raw materials in food packaging, both 42 natural and synthetic (Booth, 1990). Apart from the polymer, an adhesive formulation 43 may contain the carrier , plasticizers, tackifiers, thickeners, fillers, surfactants, biocides 44 and fungicides, emulsifiers, waxes and antioxidants (Ashley et al. 1995). ee 45 rP 46 The study of adhesives is a difficult task for many reasons: a) There are many different 47 formulations and standardization is not possible; b) There are a wide variety of 48 substrates, such as plastics, paper and board, aluminium foil, cork or wood; c) The 49 number of compounds involved in the adhesives formulation is very high and no 50 information is provided about them by the companies; d) Migration behaviour is 51 unknown and has never been tested. Adhesives are not as yet regulated mainly due to 52 these difficulties. Only in extremely limited cases such as the polyurethane based 53 adhesive layers, a clear legal restriction appears, specifically for aromatic amines, which 54 migration restriction is ‘non-detectable’ at 0.010 mg/kg (Commission Directive 55 2002/72/EC and Directive 19/2007/EC). iew ev On 56 rR 57 All these facts highlight a strong need to develop a solution for this problem, and for 58 this reason, the European Commission decided to finance the EU Project Migresives, in 59 which frame the work reported here has been carried out [www.migresives.eu]. ly 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 60 61 The analysis of adhesives is the first step to find out which substances could diffuse 62 throughout the different layers and migrate to the food in contact with them (Gruner and 63 Piringer et al. 1999). Nowadays it is well accepted that molecules of molecular mass 64 lower than 1000 daltons can migrate (Figge 1996, Jickells 1997), both in direct and 65 indirect contact with the food, as the diffusion rates are high enough to cross the barrier http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 3 of 25 66 of the materials. Diffusion rates are higher for volatile compounds, for this reason, the 67 volatiles are the priority migrants to be studied. 68 69 Several analytical procedures can be used for screening the potential volatile migrants 70 coming from the adhesives. The determination of potential migrants in a food contact 71 material usually involves an extraction step followed by the analysis using a 72 chromatographic method. However, sample handling is often time-consuming for fast 73 screening procedures. The methods based on the direct analysis of the headspace by gas 74 chromatography-mass spectrometry (GC-MS) permit the fast identification of migrants 75 with a minimum sample handling but they usually does not provide enough sensitivity 76 (Nerín et al, 2000). Advanced analytical techniques such as GC-TOF-MS (time of 77 flight) provide an accurate mass measurement of ions in mass spectra (Mamyrin 2000) 78 and for this reason has been widely used to identify target and non-target compounds 79 (Marsman et al.2008, Marsman et al. 2007, Setkova et al. 2007, Bianchi et al.2007, Hao 80 et al. 2005, Meruva et al.2004). This technique combined with ChromaLynx software, 81 able to deconvolve complex mass spectra, allows a reliable identification of the 82 compounds and it was used in this work in order to identify the compounds present in 83 the pure adhesives. Fo 84 iew ev rR ee rP 85 An alternative for screening purposes is the analysis of the headspace by solid phase 86 microextraction (HS-SPME) coupled to GC-MS. HS-SPME offers several advantages 87 versus other methods (Pawliszyn 1997, Pawliszyn 1999, Wercinski 1999), mainly a 88 considerably improvement of the sensitivity (Nerín et al, 2008), for this reason, it has 89 been shown as a powerful tool to analyse different solid and liquid samples (Yang et 90 al.2008, da Silva 2008, Pena 2008 , Batlle et al, 2001; Nerín et al, 2002; Lopez et al. 91 2006, Domeno et al. 2005, Salafranca et al. 1999 and Batlle et al. 1999). In this work, 92 HS-SPME-GC-MS was used in the screening of laminates, since they contained a low 93 quantity of adhesive and a high sensitivity was necessary. ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Food Additives and Contaminants 94 95 Materials and methods 96 Materials and reagents 97 Three acrylic adhesives were selected for this study (adhesive 1, 2 and 3) and they were 98 supplied by three adhesive companies. They were representative of commonly used 99 adhesives in commercial food packaging but their origin and main characteristics are http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 4 of 25 Food Additives and Contaminants 100 confidential and cannot be explained here. The laminates studied in this work were 101 either supplied by the companies or prepared in the laboratory: Laminate 1 was 102 prepared with adhesive 1 (grammage 45 g m-2) between aluminum foil and polyethylene 103 (PE) (40 m thickness); laminate 2 was made using the adhesive 2 (grammage 18 g m-2) 104 between polypropylene (PP) ( 25 m thickness) and PE (40 m thickness); and laminate 105 3 was made using the adhesive 3 (grammage 12 g m-2) with polypropylene (17.5 m 106 thickness) and paper ( 70 m thickness). 107 Fo 108 Three different SPME fibers were used in this work, 65 µm PDMS/DVB, 85 µm 109 Polyacrylate and 100 µm PDMS. Fibers were supplied by Supelco (Bellefonte, PA, 110 USA). Acetonitrile was from J.T. Baker (Deventer, The Netherlands). 1-Hexanol-2- 111 ethyl, 2-ethylhexylacetate, 2-ethylhexylacrylate, ethanol, 2-2(butoxyethoxy), dimethyl 112 adipate, ethanol, 2-2(butoxyethoxy) acetate and 2,4,7,9-tetramethyl-5-decyne-4,7-diol 113 standards were supplied by Sigma-Aldrich (St. Lois, MO, USA). 114 rR ee rP 115 Sample preparation 116 For the GC-TOF-MS analysis, 1 g of pure adhesive sample (non cured) was extracted 117 with 10 g of acetonitrile. Then, this solution was filtered using 0.22 µm pore size filters 118 in order to remove the acrylic polymer that had precipitated when the acetonitrile was 119 added. After this step, samples were diluted 1/100 with acetonitrile and directly injected 120 into the GC. iew ev 121 122 For the HS- GC-MS and HS-SPME-GC-MS analysis, 1cm x 1cm laminates prepared 123 from the pure materials and using about 20 g.m-2 of adhesive were cut and placed into 124 20 mL headspace vials. ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 125 126 For the migration studies a cell consisting of two plates of aluminium, among which a 127 constant pressure could be applied was used. Two films of PE (40µm) were placed at 128 each side of the laminateand this stack was placed between the plates and stored at 40ºC 129 for one hour. Then the cell was opened and each PE film was placed in 20 mL vials and 130 analysed by HS-SPME-GC-MS. Virgin PE films were also analysed with the same 131 technique. http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 5 of 25 132 Calibration curves were prepared placing the same amount of PE in 20 mL vials and 133 adding over it 10 L of the standards solution at different concentration levels. Once the 134 equilibrium was reached these vials were analysed by HS-SPME-GC-MS. 135 136 Instrumental 137 GC-TOF-MS electron ionization and chemical ionization modes 138 A GCT Premier from Waters Corporation (Milford, MA, USA) was used in both 139 electron ionization (EI) and positive chemical ionization (PCI) modes, the column used 140 was a Rtx 225 30m x 0.25mm x 0.25µm and the volume injected was 2µl. Other 141 parameters used are shown in table 1. Fo rP 142 143 HS-GC-MS and HS-SPME-GC-MS 144 A CTC Analytics CombiPal autosampler from Agilent was used. The autosampler was 145 coupled to a 5975B Agilent gas chromatograph connected to a 6890N mass 146 spectrometer , the parameters selected for the HS and the SPME analysis are shown in 147 table 2. 148 ev rR ee 149 Results and discussion 150 GC-TOF-MS electron ionizaton and chemical ionization modes 151 The first step in the screening was to study the pure adhesive formulations in their liquid 152 state. Liquid extraction with acetonitrile was applied to the adhesive and GC-MS-TOF 153 was used for the analysis after removing the precipitated polymeric phase by filtration. 154 Electron ionization (EI) was used initially and chemical ionization was further applied 155 to confirm the compound assignments and to check the reliability of the system for 156 screening. The same procedure was applied to all the adhesive samples. Figure 1 shows 157 the chromatogram obtained from the pure adhesive 3 extract using GC-TOF-MS in 158 electron ionization mode. Table 3 lists the compounds identified by this method in the 3 159 adhesives. Deconvolution of the peaks and identification of the compounds were done 160 using Chromalynx combined with NIST 08 library. This software establishes a list of 161 the most feasible candidates according to the match factor obtained comparing the mass 162 spectrum of the unknown compound with those contained in the NIST database. The 163 match factor is a measure of the certainty of the library search result and ranges from 0 164 to 1000. Afterwards, for the 5 fragments the most abundant of the spectrum, it 165 calculates the mass difference ( mDa) between the accurate masses of the detected iew ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Food Additives and Contaminants http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants 166 fragments and the accurate masses of the candidate fragments. With all these data the 167 software assigned or did not assign identification for the compound. 168 169 EI columns in table 3 show the molecular formula of the main fragment, its accurate 170 mass and the mass difference between the experimentally obtained mass fragment and 171 the theoretical mass value of the proposed compound. Even though table 3 shows the 172 data for the main fragment, mass difference was calculated for five fragments in each 173 compound. This technique enabled a reliable identification even for those compounds 174 with a low match. A total of 42 volatiles were detected by EI in the adhesives studied. 175 Most of the compounds found were esters, probably coming from the polymer involved 176 in the formulation; some alcohols, alkanes and alkoxy groups were also found. Four 177 halogenated compounds were found in adhesives 1 and 3. Fo rP 178 ee 179 To confirm the identification and complete as much as possible the screening, chemical 180 ionization (CI) GC-TOF-MS was applied to the acetonitrile extracts. Figure 2 shows the 181 chromatogram obtained from the pure adhesive 3 extract using GC-TOF-MS in CI 182 mode. In the CI mode pseudo molecular ions [M+H]+ are detected, being the molecular 183 mass a good confirmation of the compound. Again the identification was based on the 184 comparison between the theoretical accurate mass of the proposed compound and the 185 experimental accurate mass, and the match factor from EI experiments. This technique 186 allowed us to identify 14 unknown compounds and in addition, it was possible to 187 confirm 17 compounds previously identified. A total of 56 compounds were detected, 188 even though the three adhesives were acrylic based, only 9 of the volatiles were found 189 in more than one sample. These results showed the variability of adhesive formulations 190 even though the three samples were acrylic-base and some similarities could be 191 expected. This gives an idea of the complexity of the adhesives and emphasizes even 192 more the importance of the study.Table 3 shows the compounds identified in the three 193 adhesives using CI mode. For some compounds CI provided a higher sensitivity than 194 EI. Some of these compounds, such as 1-1-hexanol-2-ethyl, n-butyric acid 2-ethylhexyl 195 ester or 3(2H)-isothiazolone-2-methyl were found in adhesives where they had not been 196 detected by EI. New compounds were also found by CI such as 4-heptanone, 3-methyl, 197 2-propanone, 1-bromo, acetic acid,2-ethylhexyl ester, guanidine, 2-propenoic acid,2- 198 ethylhexyl ester, hexanoic acid, 2-ethyl-,2-methylpropyl ester, 2,5-pyrrolidinedione, 1- 199 (benzoyloxy)-, iew ev rR ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Page 6 of 25 ethanol2(2butoxyethoxy), ethanol,2(2-butoxyethoxy) http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk acetate, 1- Food Additives and Contaminants Page 7 of 25 200 dodecanol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol and phenol 2,4-bis(1,1-dimethylethyl). 201 Toxtree v 1.51 (Ideaconsult LTD) was used to estimate the toxicity according to Cramer 202 rules (Cramer 1978). Cramer rules classify the compounds in three levels of toxicity 203 depending on its chemical structure and propose a maximum daily intake for each 204 compound depending on its toxicity. The maximum intake is 3.0, 0.91 and 0.15 205 mg/bodyweight Kg/day for class I, II and III respectively. Some of the compounds 206 found in these adhesives, such as guanidine or 2,4,7,9-tetramethyl-5-decyn-4,7-diol and 207 phenol 2,4-bis(1,1-dimethylethyl) had a high toxicity (Class III, Cramer list). 2,4,7,9- 208 Tetramethyl-5-decyn-4,7-diol, nevertheless, was considered as moderate toxic by EPA 209 that means a LOAEL (lowest observed adverse effect level) of 200mg/Kg/day. From 210 this study, it could be confirmed that GC-TOF-MS is a powerful tool for adhesives 211 screening. The use of 2 different ionization modes allowed a more reliable identification 212 of the compounds detected. However, once the adhesive has been applied to the 213 substrates and cured the extraction with acetonitrile will not be so exhaustive and 214 another screening methodology with higher sensitivity, especially for the more volatile 215 compounds, is necessary. For these reason, HS-SPME-GC-MS analysis were carried 216 out. Fo 217 ev rR ee rP 218 HS-GC-MS and HS-SPME-GC-MS 219 Once the pure adhesives were analysed, HS-GC-MS and HS-SPME-GC-MS techniques 220 were used for screening the volatile compounds released by the laminates prepared with 221 these adhesives. On 222 iew 223 Headspace GC-MS is the most commonly applied technique for the screening of 224 volatile compounds when concentrations are high, as only a portion of the vapour in 225 equilibrium is analysed, while the technique based on SPME is used at lower 226 concentration levels since it is more sensitive due to the pre-concentration step that 227 takes place before injection into GC-MS. Both techniques were checked in this case for 228 screening purposes and applied under the experimental conditions described above. ly 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 229 230 The HS-SPME-GC-MS technique is based on the sorption properties of the stationary 231 phase bonded to the microfiber, and therefore the selection of the appropriate microfiber 232 is a key point. The first step was the selection of the SPME fibres and the optimization 233 of the parameters for the HS-SPME analysis. This optimization was done for one of the http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants 234 adhesives. As all the samples studied were acrylic adhesives and had similar chemical 235 characteristics, the optimized method was applied to all of them. 236 Three SPME fibers were checked for the optimization, a polyacrylate fiber, a PDMS 237 fiber and a PDMS/DVB fiber. Finally, the polyacrylate fiber was selected for the study 238 since it showed the best sensitivity and the highest number of compounds detected 239 (Figure 3). 240 241 The number of compounds detected with the polyacrylate fiber was higher than the 242 number of compounds detected by HS-GC-MS, and the intensity of the peaks was also 243 higher when using the SPME. This result confirmed that SPME was much more 244 sensitive as even compounds present at very low concentration in the laminate, where 245 the amount of adhesive was about 2 mg, were detected. Therefore this technique was 246 selected to study the adhesives composition. Fo ee rP 247 248 The software MODDE 6.0 (Umetrics AB) was used for the optimization of the 249 parameters for the HS-SPME and a Plackett Burman model was selected for this 250 purpose. Three variables were optimized: extraction time (5-30 min), extraction 251 temperature (40-80ºC) and desorption time (1-10 min).Finally, the optimum conditions 252 were as follows: extraction temperature 80ºC, extraction time 25 minutes and desorption 253 time 1 minute. 254 iew ev rR 255 The compounds identified using this method are shown in Table 4. Comparing these 256 data with those obtained by GC-TOF-MS, a considerably reduced number of substances 257 were found in SPME. This could be expected, since the samples analysed by SPME 258 were laminates, with a low quantity of adhesive (about 2 mg), while pure adhesives 259 were analysed by GC-TOF-MS. Some of the compounds found such as 1-hexanol-2- 260 ethyl and 2-ethylhexylacetate were probably impurities of the monomers used to form 261 the polymer and 2 propenoic acid, 2-ethylhexyl ester were residual monomers. Other 262 compounds found were common additives used in adhesive formulations, 1-dodecanol 263 is used combined with the monomer to form the polymer, and 2,4,7,9-tetramethyl-5- 264 decyne-4,7-diol is a surfactant .. ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Page 8 of 25 265 266 Analytical features obtained for some compounds are shown in table 5. Good detection 267 limits were obtained, all of them below 0.8 ng/dm2 and reproducibility was always http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants Page 9 of 25 268 below 9% with an average value of around 6%. These results confirm that HS-SPME- 269 GC-MS is a valuable tool for the screening of volatile compounds coming from 270 laminates, since it allows detecting compounds at very low concentration levels. 271 272 Migration studies and quantitative values 273 The presence of many compounds in the packaging material does not necessarily imply 274 that they will migrate. In fact, it is expected that most of them remain in the adhesive or 275 in the material layers at both sides of the adhesive. Therefore a migration test will be 276 necessary. Since some of the laminates were manufactured using paper in one side, 277 liquid simulants could not be used for the tests. For this reason, PE was used as receptor 278 for a quick test of the “migration potential” of the compounds identified in the 279 laminates, as it is well known that in general compounds diffuse very fast through it. 280 The test was carried out at 40ºC simulating the conditions used in migration tests for 281 food contact materials at room temperature (Council Directive 82/711/EEC). PE was in 282 contact with the laminate for 1 hour since it was observed that this time was enough for 283 the compounds to reach the equilibrium. Nevertheless it should be taken into account 284 that due to the low polarity of PE, the migration of very polar compounds could be 285 underestimated with this test. The results from these migration studies are shown in 286 table 5. None of the detected compounds were found previously in the virgin PE films. 287 As it can be seen, the concentrations ranged from 0.04 to 1.6 µg/dm2 (0.11 to 4.4 µg/g) 288 of PE in the PP side and from 0.27 to 28 µg/dm2 (0.74 to 75 µg/g) in the paper side. The 289 concentration of the compounds was always higher in the paper side, as it was expected 290 due to the porosity of the paper. The most toxic compound detected in the screening, 291 2,4,7,9-tetramethyl-5-decyne-4, was not found in none of the sides. After applying a 6 292 dm2 to 1 kg food simulant conversion factor (Directive 82/711/EEC) the maximum 293 value found in the PP side, that will be the side in contact with the food, was 9.8 µg/Kg 294 of polyethylene, being 10 µg/Kg the maximum migration value which has been 295 accepted as of no concern (Directive 2007/19/EC) This study proved that the HS- 296 SPME-GC-MS technique could be used for screening purposes as well as for 297 quantitative determination in migration studies from solid materials, even to quantify 298 levels of non concern. The determination of diffusion and partition coefficients, which 299 are important data for migration modelling, can be also determined by applying this 300 technique. Fo iew ev rR ee rP ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 301 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 10 of 25 Food Additives and Contaminants 302 303 Conclusions 304 Two analytical techniques, the GC-TOF-MS and HS-SPME-GC-MS were optimized for 305 screening the volatile compounds coming from the adhesives used in real packaging 306 materials such as laminates. A huge variability of compounds was found among the 307 adhesives studied. Both techniques provided useful information, nevertheless, the HS- 308 SPME-GC-MS was selected for the future study of migration processes, as it was a fast, 309 reliable and very sensitive method and it did not require sample handling. 310 Fo 311 Acknowledgements 312 This work has been supported by the European Union under the Collective Research 313 Programme Contract No. COLL-CT2006-030309 MIGRESIVES. The findings and 314 conclusions in this paper are the responsibility of the authors alone and should not be 315 taken to represent the opinion of the European Commission. Financial support has been 316 received also from Grupo Consolidado de Investigación T-10 from Gobierno de 317 Aragón, Spain. E. Canellas acknowledges the grant from Gobierno de Aragón. iew ev rR ee rP ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 11 of 25 318 319 References 320 321 Ashley RJ, Cochran MA, Allen KW. 1995. Adhesives in packaging. Int. J. Adhesion 322 and Adhesives 15: 101-108. 323 324 Batlle R, Sanchez C, Nerin C. 1999. A systematic approach to optimize solid-phase 325 microextraction. Determination of pesticides in ethanol water mixtures used as food 326 simulants. Analytical Chemistry 71: 2417-2422. Fo 327 rP 328 Bianchi F, Careri M, Conti C, Musci M, Vreuls R. 2007. Comparison of comprehensive 329 two-dimensional gas chromatography time-of-flight mass spectrometry and gas 330 chromatography-mass spectrometry for the qualitative characterisation of roasted barley 331 by solid-phase microextraction. Journal of Separation Science 30: 527-533 332 rR ee 333 Booth K. 1990. Industrial Packaging Adhesives. Blackie. ISBN 0216927951, 334 9780216927957 ev 335 336 Council Directive 82/711/EEC laying down the basic rules necessary for testing 337 migration of the constituents of plastic materials and articles intended to come into 338 contact with foodstuffs. 339 iew 340 Cramer GM, Ford RA, Hall RL. 1978. Estimation of Toxic Hazard. A Decision Tree 341 Approach. J. Cosmet. Toxicol 16: 255-276 342 On 343 da Silva GA, Augusto F, Poppi RJ. 2008 .Exploratory analysis of the volatile profile of 344 beers by HS-SPME-GC. Food Chemistry 111: 057-1063 ly 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Food Additives and Contaminants 345 346 Domeño C, Munizza G, Nerin C. 2005. Development of a solid-phase microextraction 347 method for direct determination of pentachlorophenol in paper and board samples: 348 Comparison with conventional extraction method. Journal of Chromatography A, 1095: 349 8-15 350 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants 351 European Commission. Directive 2002/72/EC relating to plastic materials and article 352 intended to come into contact with foodstuffs. 353 354 European Commission. Directive 2007/19/EC Commission Directive of 2 April 2007 355 amending Directive 2002/72/EC relating to plastic materials and articles intended to 356 come into contact with food and Council Directive 85/572/EEC laying down the list of 357 simulants to be used for testing migration of constituents of plastic materials and articles 358 intended to come into contact with foodstuffs. Fo 359 360 Figge, K. 1996. Plastic Packages for Foodstuffs (Stuttgart:Wissenschaftliche) rP 361 362 Gruner A, Piringer O. 1999. Component migration from adhesives used in paper and 363 cardboard packaging for foodstuffs. Packag. Tecnol. Sci. 12: 12-28 ee 364 365 Hao CY, Headley JV, Peru KA, Frank R, Yang P, Solomon KR. 2005. Characterization 366 and pattern recognition of oil-sand naphthenic acids using comprehensive two- 367 dimensional gas chromatography/time-of-flight mass spectrometry. Journal of 368 Chromatography A 1067: 277-284 369 iew ev rR 370 Jickells, S.M. 1997. Possible control measures for paper and board. Work shop on paper 371 and board in food contact applications, 28-29, European commission Joint Research 372 Centre. 373 On 374 Lopez P, Huerga MA, Batlle R, Nerin C. 2006. Use of solid phase microextraction in 375 diffusive sampling of the atmosphere generated by different essential oils. Analytica 376 Chimica Acta 559: 97-104 377 ly 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Page 12 of 25 378 Mamyrin B.A. 2000. Time of flight mass spectrometry (concepts, achievements and 379 prospects). International Journal of Mass Spectrometry 206: 251-266. 380 381 Marsman JH, Wildschut J, Evers P, de Koning S, Heeres HJ. 2008. Identification and 382 classification of components in flash pyrolysis oil and hydrodeoxygenated oils by two- 383 dimensional gas chromatography and time-of-flight mass spectrometry. Journal of 384 Chromatography A. 1188: 17-25 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants Page 13 of 25 385 386 Marsman JH, Wildschut J, Mahfud F, Heeres HJ. 2006. Identification of components in 387 fast pyrolysis oil and upgraded products by comprehensive two-dimensional gas 388 chromatography and flame ionisation detection. Journal of Chromatography A 1150: 389 21-27 390 391 Meruva NK, Penn JM, Farthing DE. 2004. Rapid identification of microbial VOCs from 392 tobacco molds using closed-loop stripping and gas chromatography/time-of-flight mass 393 spectrometry. Journal of Industrial Microbiology & Biotechnolog 31: 482-488 Fo 394 rP 395 Nerín C, Salafranca J, Aznar M and Batlle R. 2009. Critical review on recent 396 developments in solventless techniques for extraction of analytes. Analytical and 397 Bioanalytical Chemistry 393:809–833 398 Nerín C, Rubio C, Salafranca J, Batlle R. 2000. The simplest sample treatment 399 techniques to assess the quality and safety of food packaging materials. Reviews in 400 Analytical Chemistry 19: 435-465. 401 Nerín C, Philo MR, Salafranca J, Castle L. 2002. Determination of bisphenol–type 402 contaminants from food packaging materials in aqueous foods by solid-phase 403 microextraction-high-performance liquid chromatography. Journal of Chromatography 404 A 963: 375-380. 405 iew ev rR ee On 406 Pawliszyn J. 1997. Solid Phase Microextraction: Theory and Practice,Wiley-VCH, New 407 York 408 ly 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 409 Pawliszyn J. 1999. Application of solid phase Microextraction, Royal Society of 410 Chemistry, Cambridge. 411 412 Pena RM, Barciela J, Herrero C, Garcia-Martin S. 2008. Headspace solid-phase 413 microextraction gas chromatography-mass spectrometry analysis of volatiles in orujo 414 spirits from a defined geographical origin. Journal of agricultural and food chemistry 415 56: 2788-2794 416 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 14 of 25 Food Additives and Contaminants 417 Resolution AP (2002) on paper and board materials and articles intended to come in 418 contact with food stuff 419 420 Salafranca J, Batlle R, Nerin C. 1999. Use of solid-phase microextraction for the 421 analysis of bisphenol A and bisphenol A diglycidyl ether in food simulants. Journal of 422 Chromatography A 864: 137-144 423 424 Setkova L, Risticevic S, Pawliszyn J. 2007. Rapid headspace solid-phase 425 microextraction-gas chromatographic-time-of-flight mass spectrometric method for 426 qualitative profiling of ice wine volatile fraction - I. Method development and 427 optimization. Journal of Chromatography A 1147: 213-223. Fo rP 428 429 Wercinski A.S. 1999. Solid Phase Microextraction: A practical Guide, Marcel Dekker, 430 New York. rR 431 ee 432 Yang ZY, Maruya KA, Greenstein D, Tsukada D, Zeng EY. 2008. Experimental 433 verification of a model describing solid phase microextraction (SPME) of freely 434 dissolved organic pollutants in sediment porewater. Chemosphere 72: 1435-1440 435 437 438 440 441 ly On 439 iew 436 ev 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants Page 15 of 25 Table 1: Instrument parameters for the GC-TOF-MS analysis Instrumentation Ionization mode GC conditions MS conditions Gas flow (ml min-1) Injector (ºC) Oven Ionization mode Mass range Reaction gas EI 1 230,splitless 60ºC, 5min; 5ºC min-1; 220ºC 6min EI+ 50-800 No CI 1 230,splitless 60ºC, 5min; 5ºC min-1; 220ºC 6min CI+ 50-800 Methane Fo iew ev rR ee rP ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 16 of 25 Food Additives and Contaminants Table 2. Instrument parameters for the HS- GC-MS and HS-SPME-GC-MS analysis Instrumentation CombiPal HS CombiPal HS-SPME Fo GC conditions MS conditions Preincubation time (s) Incubation Temperature (ºC) Volume extracted (mL) 120 80 1 Preincubation time (s) Incubation Temperature (ºC) Extraction time (s) Desorption time (s) Postfiber condition time (s) 120 80 1500 60 1200 Column Gas flow (ml min-1) Injector (ºC) Oven DB-5(30 mx0.25 mm,0.25 um) 1.5 250,splitless 40ºC, 5min; 10ºC min-1; 300ºC 1min 45-400 230 150 70 rP Mass range Source (ºC) Quadrupole (ºC) Electron energy (eV) iew ev rR ee ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 17 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Food Additives and Contaminants Table 3: Compounds identified in adhesives 1, 2 and 3 by GC-TOF-MS in EI and CI modes, retention times (RT), identification number of the compounds in figures 1 and 2 (No), molecular formula, match factor; main fragment formula, its accurate measured mass and mDa for the EI mode; accurate measured mass of MH and mDa for the CI mode ( mDa was calculated referred to the theoretical mass from NIST database) RT Compounds (min) 5.1 Fo Adhesive rP No 5.13 2-propenoic acid, 2methylpropyl ester 2-propenoic acid,methyl ester 2 5.2 4-heptanone 2 5.4 2 5.83 propanoic acid,2-methyl,butyl ester 4-heptanone, 3-methyl 2 5.89 2-propanone, 1-bromo 3 5.9 6.4 biclyclo[2.2.1]heptan-2-ol, 2(2-cyclopenten-1-yl)butanoic acid,butyl ester 6.46 2 ee EI Main fragment Accurate formula mass C3H3O 55.0160 Molecular formula Match factor C7H12O2 817 C4H6O2 748 C7H14O 926 C4H7O 71.0480 C8H16O2 786 C4H9O2 89.0600 rR ev CI Accurate mass (MH) mDa 87.0447 0.1 -1.7 115.1131 0.8 -0.3 145.1231 0.3 129.1280 0.1 136.9687 8.5 145.1248 2.0 mDa -2.4 C8H16O 856 C3H5BrO 891 1 C12H18O 633 C4H5O 69.0331 -0.9 2 C8H16O2 932 C4H7O 71.0452 -4.5 butanoic acid,butyl ester 2 C8H16O2 911 6.7 pyrazine,2,6-dimethyl- 2 C6H8N2 758 C6H8N2 108.0678 -0.9 7.2 4-methoxy-oxazolidin-2-one 2 C4H7NO3 685 C4H6O2 86.0359 -0.9 7.7 1-butoxy-2-ethylhexane 1 C12H26O 847 C4H9 57.0700 -0.4 187.2049 -1.3 8.4 2-butenoic acid, butyl ester 2 C8H14O2 852 C4H7O2 87.0410 -3.6 143.1106 3.4 9.1 cyclohexanol, 1-butyl- 1 C10H20O 632 C7H15 99.1187 1.3 9.1 1-hexanol-2-ethyl- 131.1377 -5.9 9.1 9.1 1 iew On ly 1/3 2 C8H18O 795 C6H11 83.0753 -10.8 6-dodecanone 3 3 C12H24O 631 C4H10 58.0779 -0.4 cycloheptanol 3 4 C7H14O 561 C3H5O 57.0375 3.5 http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Page 18 of 25 9.1 1-decanol 3 5 C10H22O 807 C6H11 83.0757 -10.4 9.1 1-hexene,2,5-dimethyl- 3 6 C8H16 740 C4H8 56.0598 -2.8 9.7 acetic acid,2-ethylhexyl ester 1/3 7 C10H20O2 864 9.7 1-pyrrolidinyloxy,3-amino2,2,5,5-tetramethylbenzaldehyde 3 8 C8H17N2O 644 C4H8N 70.0659 0.2 C7H6O 844 C7H5O 105.0341 0.1 C24H39FO2 791 C9H17O 141.1276 -0.3 C8H16O3 901 C4H7O2 87.0446 0.0 9.9 10.1 Fo 10.3 2-fluorobenzoic acid, heptadecyl ester 2-butoxyethyl acetate 10.5 guanidine 10.8 10.9 2-fluorobenzoic acid, undecyl ester benzene, 1,3,5-triethyl- 11.5 propanoic acid, octyl ester 11.8 2-propenoic acid,2-ethylhexyl ester hexanoic acid, 2-ethyl-,2methylpropyl ester 2,5-pyrrolidinedione, 1(benzoyloxy)n-butyric acid 2-ethylhexyl ester octane, 3-ethyl- 12.3 13.0 13.4 13.8 14.4 15.2 15.9 16.2 cyclopentane,(2methylbutylidene)ethanol2(2butoxyethoxy) 3-hydroxypropanoic acid 1butyl ester decane,1-bromo- rP 1/2 1/3 3 1/2 1 9 ee 10 1 rR C24H39FO2 949 C18H27FO2 767 ev C9H17O 141.1272 -0.7 173.1552 1.1 107.0504 0.7 161.1207 3.0 60.0481 -8.0 C12H18 939 C10H13 133.1008 -0.9 163.1497 1.0 C11H22O2 754 C5H10 70.0689 -9.4 187.1695 -0.3 C11H20O2 856 185.1541 0.0 1 C12H24O2 829 201.1835 -1.9 2 C11H9NO4 964 220.0610 0.0 C12H24O2 859 C4H7O 71.0498 0.1 201.1805 -4.9 1 C10H22 828 C8H16 112.1238 -1.4 1 C10H18 691 C8H13 109.1011 -0.6 C8H18O3 800 163.1243 -9.1 C7H14O3 588 C3H5O3 89.0229 -1.0 C10H21Br 900 C4H8[81Br] 136.9800 1.1 1/3 11 3 12 1/3 3 13 14 2 3 15 iew On ly http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 19 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Food Additives and Contaminants 16.2 undecane,1-bromo 3 16 C11H23Br 813 235.1120 5.8 18.5 ethanol,2(2-butoxyethoxy) acetate 2-butanone,4-(acetyloxy)- 3 17 C10H20O4 913 205.1325 -11.5 3 18 C6H10O3 709 C4H7O2 87.0447 0.1 1/3 19 C4H4ClNOS 835 C4H4NOS[35Cl] 148.9703 0.1 149.9791 1.1 C12H26O 879 C6H11 83.0857 -0.4 187.2096 3.4 227.2011 0.0 116.0137 -3.3 221.1389 0.0 207.1749 0.0 195.1021 0.0 19.1 19.2 19.3 20.5 20.9 21.4 21.4 22.2 23.1 23.2 23.2 23.4 25.3 25.5 25.8 27.2 Fo 5-chloro-2-methyl-3(2H)isothiazolone 1-dodecanol 2,4,7,9-tetramethyl-5-decyn4,7-diol 3(2H)-isothiazolone, 2methylcyclopentane,1,2,3-trimethyl,(1a,2a,3a)3,7-dioxo-4,8-dioxa-10-ethyl1-tetradecanol 2-[2-(2-ethoxyethoxy) ethoxy]ethyl acetate 2-butenedioic acid (z)-, dibutyl ester phenol 2,4-bis(1,1dimethylethyl) pentanoic acid, 5-hydroxy,2,4-t-butylphenyl esters benzoic acid,4-ethoxy-,ethyl ester 2-[2-(2-butoxyethoxy) ethoxy]ethyl acetate hexanedioic acid, 3-methyl,dibutyl ester 4,4’-bi-1,3,2-dioxaborolane, 2,2’-diethyl-,(R*,S*)phenol, 4-(1,1,3,3- rP 20 C14H26O2 792 21 C4H5NOS 881 C4H5NOS 115.0019 -7.3 3 22 C8H16 718 C5H10 70.0753 -3.0 C3H5O2 73.0237 -5.3 2 3 1/3 ee 3 23 3 rR ev C14H26O5 712 24 C10H20O5 844 C4H7O2 87.0441 -0.5 3 25 C12H20O4 886 C4H3O3 99.0080 -0.2 3 26 C14H22O 883 3 27 C19H30O3 886 C13H19O 191.1444 0.8 3 28 C11H14O3 872 C7H5O2 121.0291 0.1 3 29 C12H24O5 816 C4H7O2 87.0444 -0.2 2 C15H28O4 670 C7H11O3 143.0709 0.1 1 C8H16B2O4 722 C5H7O2 99.0439 -0.7 1 C14H22O 932 C9H11O 135.0804 -0.6 iew On ly http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Page 20 of 25 tetraamethylbutyl)27.6 benzophenone 3 30 C13H10O 913 C7H5O 105.0337 Fo rP ee rR ev iew On ly http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk -0.3 Page 21 of 25 Table 4. Compounds identified by HS-SPME-GC-MS in adhesives 1, 2 and 3, retention times (RT) and identification number of the compounds in figure 3 (No). RT (min) 9.2 10.72 11.9 12.3 12.8 13.4 13.6 14.0 14.1 15.3 16.0 16.1 16.1 16.7 17.3 22.97 23.25 Compounds Adhesive benzaldehyde 1-hexanol- 2-ethyl undecane benzene ,1,3,5-triethyl acetic acid, 2-ethylhexyl ester 2-ethylhexylacrylate 1-butoxy-2-ethylhexane ethanol, 2-2(butoxyethoxy) dimethyl adipate n-butyric acid, 2-ethylhexyl ester ethanol, 2-2(butoxyethoxy) acetate propanoic acid, 2-methyl-,hexyl ester 3-hydroxypropanoic acid 1-butyl ester 2,4,7,9-tetramethyl-5-decyne-4,7-diol 1-dodecanol butanoic acid, butyl ester hexanedioic acid, 3-methyl-,dibutyl ester Fo 2 1/3 2 1 1/3 3 1 3 3 1 3 2 2 3 2 2 2 No 1 2 3 4 5 6 7 iew ev rR ee rP ly On 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Food Additives and Contaminants http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk 6 Food Additives and Contaminants 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Page 22 of 25 Table 5. Concentration of the compounds found in PE from migration experiments expressed as g/dm2 of PE and as g/g of PE, limits of detection (LOD) expressed as ng/dm2 of PE and RSD (%) of the analytical method. 1-hexanol-2-ethyl 2-ethylhexylacetate Ethanol-2(2 butoxyethoxy) 2-ethylhexylacrylate Dimethyladipate Ethanol 2(2butoxyethoxyacetate) 2,4,7,9-tetramethyl-5decyne-4 laminate PP side ( g/dm2) 0.04 0.05 0.17 laminate PP side ( g/g) 0.11 0.13 0.46 0.04 0.07 1.6 0.11 0.18 4.4 Fo n.d. n.d. non detected in the migration experiment rP laminate paper side (µg/dm2) 0.34 1.2 3.2 laminate paper side (µg/g) 0.93 3.3 8.7 LOD (ng/dm2) 0.79 0.39 0.59 RSD (%) 5.5 6.2 6.7 0.58 0.27 28 1.5 0.74 75 0.39 0.79 0.39 5.3 5.4 8.3 n.d. n.d. 0.59 6.0 8 2 0 3 ee n.d rR 3 5 3 1 ev 7.90 .41 iew On ly http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Page 23 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Food Additives and Contaminants Fo rP ee rR ev iew On ly Figure 1.Chromatogram of adhesive 3 obtained by GC-TOF-MS and EI mode. Identification numbers explained in table 3. c http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk Food Additives and Contaminants 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Page 24 of 25 Fo rP ee rR ev iew On Figure 2. Chromatogram of adhesive 3 obtained by GC-TOF-MS and CI mode. Identification numbers explained in table 3. http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk ly c Page 25 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Food Additives and Contaminants Fo rP ee rR ev iew On ly Figure 3. Chromatogram of laminate 3 obtained by HS-SPME-GC-MS with a polyacrylate fiber Identification numbers explained in table 4. http://mc.manuscriptcentral.com/tfac Email: fac@tandf.co.uk b obtained for