Bradley and Coulier 2007

Report FD 07/01
An investigation into the reaction and

breakdown products from starting substances
used to produce food contact plastics
PROJECT INFORMATION
Report Number: FD07/01
Authors - CSL: E Bradley

Authors - TNO: L Coulier
Date: August 2007
Project title: An investigation into the reaction and breakdown

products from starting substances used to
produce food contact plastics
Sponsor: Food Standards Agency

Aviation House
125 Kingsway
London
WC2B 6NH
Sponsor’s Project Number: A03054
CSL Project Number: N6JF
CSL File Reference: FLN 8491
Principal Workers - CSL: E Bradley, M Driffield, S Jones, M Scotter and

D Speck
Principal Workers - TNO: L Coulier, R. Bas, S. Steegman, M. Tienstra and
B. Muilwijk
Team Leader: L Castle
Distribution: 1. Dr Barnes (FSA) (x3 + .pdf version)

2. CSL Library
3. Dr Dennis (CSL)
4. Prof. Gilbert (CSL)
CSL
Sand Hutton
York
YO41 1LZ
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SUMMARY
Food packaging materials made of plastics may contain substances that are not used
intentionally and do not appear in lists of permitted ingredients. They may be present
as impurities in the starting materials used to make the plastic; as reaction
intermediates formed during the polymerisation processes; or as decomposition or
reaction products formed during polymerisation to make the plastic or during thermal
processing of the plastic to make the packaging. These substances are commonly
referred to as NIAS (non-intentionally added substances). There are two categories of
NIAS. The first, although unintentional, are nevertheless known substances such as
isomers, intermediates and impurities given in the technical specifications. The second
category is those substances that are undetected or unidentified and so are unknown.
Reaction and breakdown products along with minor impurities often fall into this second
category of unknown NIAS. The main aim of this project was to identify and catalogue
the NIAS derived from starting substances used to make six major food contact
polymers.
Six polymers were prepared containing additives chosen to be representative of those

typically used in plastic materials and articles intended for contact with food. Test
plastics containing the selected additives at concentrations typically used in the
manufacture of food contact plastics were moulded into sheets. Control plastics were
also prepared in which no additives were incorporated. Five of the plastics were the
volume polymers used in packaging, namely polypropylene, polyethylene, polystyrene,
polyvinyl chloride and polyethylene terephthalate. The sixth plastic selected was nylon,
included because although it is used in lesser volumes, it finds important and
demanding applications by virtue of its good barrier properties and high temperature
resistance. It is also the only one of the six polymers that has a high content of
nitrogen built-into the polymer chain.
A database of ingredients and similes was prepared and a literature search was carried
out to establish any actual or likely reactions of the ingredients and their similes, alone
or in combination, under the conditions used to manufacture the test plastics. From
this literature search a theoretical list of possible impurities/degradation
products/reaction products was prepared for each of the plastic/additive combinations.
A suite of analytical methods focussing on the analysis of substances with molecular

weights below 1,000 Dalton, in view of toxicological significance, were applied to the
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plastics themselves and to extracts of the materials. Extracts of the plastics with and
without the additives were prepared using both polar and non-polar solvents.
Analytical methodology used included thermodesorption gas chromatography-mass
spectrometry (GC-MS) to detect very volatile substances, GC-MS and GCxGC-time of
flight (TOF)-MS to detect semi-volatile substances and liquid chromatography (LC)-
TOF-MS and LC-Fourier transform (FT)-MS to detect non-volatile substances. By
comparing the chromatograms obtained for the analysis of the plastic and additive
samples with those obtained from the analysis of the plastics only, any additional
substances present were identified. The additives used in the manufacture of the test
plastics were analysed in the same way such that any impurities present in the starting
materials were detected. Internal standards were added to the plastics prior to
extraction and the concentrations of any NIAS detected were estimated based on their
relative responses. All six plastics were also analysed by NMR. Many peaks were
detected in the chromatograms of the test plastics that were not in the controls. Some
could be attributed to the additives themselves, others were present as impurities in the
additive starting substances and several were predicted reaction/breakdown products.
However, for some plastics there remained a large number of substances that did not
fit into any of these categories. This was particularly the case for polypropylene, high
density polyethylene and polyvinyl chloride. Migration modelling was applied to
determine the significance of the levels of the unknowns estimated in the plastics, i.e.
to what extent these substances are likely to migrate. As their identities were not
known then the migration levels were estimated by assuming good solubility in the
foodstuff/food simulant.
It has long been a requirement that any chemical migration from food packaging
materials should not endanger human health. This concept is enshrined in general
terms in Article 3 of the EU Framework Regulation covering food contact materials.
The compliance of food contact plastics with Article 3 must be assessed taking into
account both (a) known ingredients and (b) their impurities, reaction products and
breakdown products. It would be fair to say that, to date, producers have focussed
mainly on the former and have largely neglected the latter.
It is now clarified in recital 13 of Directive 2007/19/EC that there is a general

requirement to assess the safety of ALL potential migrants, including impurities,
reaction and breakdown products and the onus is on the business operator to do so.
To demonstrate compliance such ‘non-listed substances’ should be assessed in
accordance with international risk assessment procedures. The Commission of the EU
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says it cannot regulate all the different combinations of substances used in food
packaging and it wants the industry to take more active responsibility in this area. The
technical problem is that neither the EU commission, Member States, or industry, really
know what is reasonably achievable in this area. On the one hand, there can be
extravagant claims that virtually each and every last molecule must be accounted for.
On the other hand, some claim that nothing useful can be achieved and the issue
should be ignored.
This project represents the state-of-the-art with two highly experienced and well-
equipped institutes bringing their combined resources to bear on this question. A
number of substances that would previously have been reported as NIAS have been
identified. However, a larger number of substances remain either unidentified or with
an ambiguous identification only. It can be concluded that for surveillance and official
enforcement laboratories this will be the situation too – the full elucidation of all NIAS
cannot be achieved to date using analytical chemistry alone.
It is certain that the responsible chemical and plastics industries could identify some
more of these substances by using their scientific and technical know-how built-up over
many years. This notwithstanding, within a reasonable resource and time allocation
the combination of theoretical predictions with the application of advanced analytical
techniques is unlikely to be capable of detecting and identifying every non-intentionally
added substance in food contact plastics.
This analytical approach would provide a useful demonstration of due diligence.

However, it may need to be considered along with other complementary approaches.
These could include concepts advocated elsewhere, such as toxicological evaluation of
the whole migrate (if feasible) and/or threshold concepts such as threshold of
regulation or thresholds of toxicological concern. However, all these would need to be
formally assessed by the European Authorities to ensure the resulting method is
appropriate, scientifically sound and reliable.
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Table of contents Page No.
1. INTRODUCTION 21
1.1 Background 21
1.2 Approach 21
1.3 Objectives 22
2. MANUFACTURE OF THE TEST POLYMERS 22
2.1 Selection of the polymer types 22
2.2 Selection of the test additives 23
2.2.1 Polypropylene 23
2.2.2 High density polyethylene 24
2.2.3 Polystyrene 24
2.2.4 Polyethylene terephthalate 25
2.2.5 Polyvinyl chloride 25
2.2.6 Polyamide 26
2.3 Manufacturing conditions of the test polymers 26
2.3.1 Compounding 26
2.3.2 Moulding 27
3. IMPURITIES, REACTION PRODUCTS AND BREAKDOWN 28
PRODUCTS OF THE SELECTED PLASTICS AND ADDITIVES
3.1 Polypropylene 28
3.1.1 General aspects of polypropylene chemistry 28
3.1.2 Diparamethylenedibenzylidene sorbitol 29
3.1.3 Tris(2,4-di-tert-butylphenyl)phosphite 30
3.1.4 Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) 31
3.1.5 Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]- 33
[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-
[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]
3.1.6 Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene 34
ethanol-alt-1,4-butanedioic acid)
3.1.7 Erucamide 35
3.1.8 Glycerol monostearate 35
3.1.9 Calcium carbonate 35
3.2 High density polyethylene 36
3.2.1 General aspects of polyethylene chemistry 36
3.2.2 Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite 37
3.2.3 Octadecyl 3,3-di-t-butyl-4-hydroxyhydrocinnamate 37
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3.2.4 Oleamide 38
3.2.5 Titanium dioxide 38
3.2.6 N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine 39
3.2.7 Glycerol monooleate 39
3.2.8 Sodium (C10-C18) alkyl sulfonate 39
3.2.9 2,5-Bis(5’-tert-butylbenzoxazol-2-yl)thiophene 39
3.3 Polystyrene 39
3.3.1 General aspects of polystyrene chemistry 39
3.3.2 Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl) 41
propionate)
3.3.3 Tris(nonylphenyl)phosphite 41
3.3.4 Di-(2-ethylhexyl) phthalate 41
3.3.5 N,N-Bis(stearoyl)ethylenediamide 42
3.3.6 Polyethylene glycol 4-tert-octyl-phenyl ether, n~5 and 42
polyethylene glycol 4-tert-octyl-phenyl ether, n=9-10
3.3.7 2-(2’-Hydroxy-5’-methylphenyl)benzotriazole 42
3.4 Polyethylene terephthalate 43
3.4.1 General aspects of polyethylene terephthalate chemistry 43
3.4.2 2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol 46
3.4.3 Hexanedioic acid polymer with 1,3-benzenedimethanamine 46
3.4.4 Copper phthalocyanine blue 47
3.5 Polyvinyl chloride 48
3.5.1 General aspects of polyvinyl chloride chemistry 48
3.5.2 Dioctyltin bis(ethylmaleate) and dioctyltin bis(2-ethylhexyl 49
thioglycolate)
3.5.3 Epoxidised soya bean oil 51
3.5.4 Stearic acid 53
3.5.5 Acetyl tributyl citrate 53
3.5.6 Paraffin wax 53
3.6 Polyamide 54
3.6.1 General aspects of polyamide chemistry 54
3.6.2 Zinc stearate 55
3.6.3 Talc 56
4. THEORETICAL LIST OF POSSIBLE IMPURITIES / 57
DEGRADATION PRODUCTS / REACTION PRODUCTS
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5. ANALYSIS OF THE TEST POLYMERS 57
5.1 Sample preparation 58
5.1.1 Sample preparation for thermodesorption GC-MS 58
5.1.2 Sample preparation for GC-MS and GCxGC-TOF-MS 58
5.1.3 Sample preparation for LC-MS, LC-FT-MS and LC-TOF-MS 59
5.1.4 Sample preparation for NMR 59
5.2 Analysis 60
5.2.1 Analysis by thermodesorption GC-MS 60
5.2.2 Analysis by GC-MS 60
5.2.3 Analysis by GCxGC-TOF-MS 61
5.2.4 Analysis by LC-MS and LC-FT-MS 62
5.2.5 Analysis by LC-TOF-MS 62
5.2.6 Analysis by NMR 63
5.2.6.1 CDCl3 extracts 63
5.2.6.2 DMSO extracts 63
5.2.6.3 2D NMR spectroscopy acquisition parameters 64
6. COMPARING THE IDENTITIES OF THE EXTRACTABLES 64
DETECTED WITH THE PREDICTED SUBSTANCES
6.1 Volatile substances detected by thermodesorption GC-MS 65
6.2 Semi-volatile substances detected by GC-MS and 66
GCxGC-TOF-MS
6.2.1 Additives 66
6.2.2 Samples 67
6.2.2.1 Polypropylene 68
6.2.2.2 High density polyethylene 69
6.2.2.3 Polystyrene 70
6.2.2.4 Polyethylene terephthalate 70
6.2.2.5 Polyvinyl chloride 71
6.2.2.6 Polyamide 72
6.2.2.7 GCxGC-TOF-MS 72
6.3 Non-volatile and polar compounds analysed by LC-MS and 73
LC-FT-MS
6.3.1 Additives 73
6.3.2 Samples 74
6.4 Non-volatile and polar compounds analysed by LC-TOF-MS 76
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6.4.1 Additives 76
6.4.2 Samples 76
6.5 NMR analysis 77
6.5.6 Polyamide 80
6.5.7 2-Dimensional NMR 80
7. MIGRATION MODELLING 83
8. CONCLUSIONS 85
8.1 Summary of findings 85
8.1.6 Polyamide 88
8.1.7 Migration potential of the NIAS 88
8.2 Additive purity and the impact on NIAS 89
8.3 Limitation on predictions of reaction and breakdown 89
products as NIAS
8.4 Limitations of analytical methods to detect, identify and 89
measure NIAS
8.5 Other assessment techniques that may be considered 90
9. REFERENCES 90
TABLES 97
FIGURES 185
ANNEX 1 272
ANNEX 2 406
APPENDIX 1 584
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List of Tables Page No.
Table 1. Formulation details of the PP test material 97
Table 2. Formulation details of the HDPE test material 98
Table 3. Formulation details of the PS test material 99
Table 4. Formulation details of the PET test material 99
Table 5. Formulation details of the PVC test material 100
Table 6. Formulation details of the PA test material 100
Table 7. List of compounds identified in virgin HDPE 101
Table 8. Organo-tin compounds present in a commercial PVC foil by 101
119
Sn Mössbauer spectroscopy
Table 9. Identified degradation products from the thermooxidation of 102
non-recycled PA 6,6
Table 10. Proposed impurities/reaction products/breakdown products for 103
the additives used in the manufacture of the PP test material
the additives used in the manufacture of the HDPE test material
the additives used in the manufacture of the PS test material
the additives used in the manufacture of the PET test material
the additives used in the manufacture of the PVC test material
the additives used in the manufacture of the PA test material
Table 16. Molecular Feature Editor (MFE) parameters used in the 121
LC-TOF-MS data analysis
Table 17. Solutions of additives in ethanol and isooctane analysed by 122
GC-MS
Table 18. Substances detected in the GC-MS TIC chromatograms of the 124
solvent extracts of the PP + additives samples that were not
present in the extracts of the PP samples
ethanol extracts of the HDPE + additives samples that were not
present in the ethanol extracts of the HDPE samples
solvent extracts of the PS + additives samples that were not
present in the extracts of the PS samples
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solvent extracts of the PET + additives samples that were not
present in the extracts of the PET samples
solvent extracts of the PVC + additives samples that were not
present in the extracts of the PVC samples
Table 23. Additional peaks observed in the concentrated ethanol extracts 154
of PP + additives with GCxGC-TOF-MS
Table 24. Overview of additives analysed by LC-MS 157
Table 25. Additional peaks observed for PP + additives with LC-MS 158
Table 26. Additional peaks observed for PS + additives with LC-MS 160
Table 27. Additional peaks observed for PET + additives with LC-MS 160
Table 28. Identities of the additional peaks observed for PP + additives 161
with LC-FT-MS
Table 29. Identities of the additional peaks observed for PS + additives 164
with LC-FT-MS
Table 30. Identities of the additional peaks observed for PET + additives 165
with LC-FT-MS
Table 31. Overview of peaks observed in the chromatograms when the 166
additives were analysed by LC-TOF-MS with +ve ESI
Table 32. Overview of peaks observed in the chromatograms when the 170
additives were analysed by LC-TOF-MS with -ve ESI
Table 33. Positive ESI analysis of the ethanol extracts of the HDPE 172
(final solvent acetonitrile) – substances that were only detected
in the HDPE + additivs extracts
Table 34. Positive ESI analysis of the isooctane extracts of the HDPE 174
in the HDPE + additives extracts
Table 35. Negative ESI analysis of the ethanol extracts of the HDPE 175
Table 36. Positive ESI analysis of the ethanol extracts of the PVC (final 176
solvent acetonitrile) – substances that were only detected in
the PVC + additives extracts
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Table 37. Positive ESI analysis of the isooctane extracts of the PVC 179
(final solvent acetonitrile) – substances that were only
detected in the PVC + additives extracts
Table 38. Negative ESI analysis of the ethanol extracts of the PVC 181
Table 39. Negative ESI analysis of the isooctane extracts of the PVC 183
Table 40. Migration modelling data 184
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List of Figures Page No.
Figure 1. Thermodesorption GC-MS chromatograms of PP and 185
PP + additives
Figure 2. Thermodesorption GC-MS chromatograms of HDPE and 186
HDPE + additives
Figure 3. Thermodesorption GC-MS chromatograms of PS and 187
PS + additives
Figure 4. Thermodesorption GC-MS chromatograms of PET and 188
PET + additives
Figure 5. Thermodesorption GC-MS chromatograms of PVC and 189
PVC + additives
Figure 6. Thermodesorption GC-MS chromatograms of PA and 190
PA + additives
Figure 7. Best library match of the peak eluting at retention time 191
11.5 minutes in the thermodesorption GC-MS chromatogram
of the HDPE + additives sample
of the HDPE + additives sample
of the PVC + additives sample
Figure 12. GC-MS chromatograms of ethanol extracts of PP and 196
PP + additives full scale and zoomed in to show low intensity
peaks
Figure 13. GC-MS chromatograms of isooctane extracts of PP and 197
PP + additives full scale and zoomed in to show low
intensity peaks
Figure 14. GC-MS chromatograms of the concentrated ethanol extracts 198
of PP and PP + additives full scale and zoomed in to show
low intensity peaks
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Figure 15. GC-MS chromatograms of ethanol extracts of HDPE and 199
HDPE + additives full scale and zoomed in to show low
intensity peaks
Figure 16. GC-MS chromatograms of isooctane extracts of HDPE and 200
HDPE + additives full scale and zoomed in to show low
intensity peaks
Figure 17. GC-MS chromatograms of concentrated ethanol extracts of 201
HDPE and HDPE + additives full scale and zoomed in to
show low intensity peaks
Figure 18. GC-MS chromatograms of the concentrated isooctane 202
extracts of HDPE and HDPE + additives full scale and zoomed
in to show low intensity peaks
Figure 19. GC-MS chromatograms of ethanol extracts of PS and 203
PS + additives full scale and zoomed in to show low intensity
peaks
Figure 20. GC-MS chromatograms of isooctane extracts of PS and 204
PS + additives full scale and zoomed in to show low intensity
peaks
PS and PS + additives full scale and zoomed in to show low
intensity peaks
Figure 22. GC-MS chromatograms of the concentrated isooctane extracts 206
PS and PS + additives full scale and zoomed in to show low
intensity peaks
Figure 23. GC-MS chromatograms of ethanol extracts of PET and 207
PET + additives
Figure 24. GC-MS chromatograms of isooctane extracts of PET and 208
PET + additives
of PET and PET + additives full scale and zoomed in to show
low intensity peaks
Figure 26. GC-MS chromatograms of the concentrated isooctane extracts 210
of PET and PET + additives. full scale and zoomed in to show
low intensity peaks
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Figure 27. GC-MS chromatograms of ethanol extracts of PVC and 211
PVC + additives full scale and zoomed in to show low intensity
peaks
Figure 28. GC-MS chromatograms of isooctane extracts of PVC and 212
PVC + additives full scale and zoomed in to show low intensity
peaks
Figure 29. GC-MS chromatograms of ethanol extracts of PA and 213
PA + additives full scale and zoomed in to show low intensity
peaks
Figure 30. GC-MS chromatograms of isooctane extracts of PA and 214
PA + additives
Figure 31. GC-MS chromatograms of concentrated ethanol extracts 215
of PA and PA + additives full scale and zoomed in to show low
intensity peaks
Figure 32. GC-MS chromatograms of concentrated isooctane extracts 216
of PA and PA + additives full scale and zoomed in to show low
intensity peaks
Figure 33. GCxGC-TOF-MS chromatograms of ethanol extracts of 217
(A) PP and (B) PP + additives
Figure 34. GCxGC-TOF-MS chromatograms of isooctane extracts of 218
(A) PP and (B) PP + additives
Figure 35. GCxGC-TOF-MS chromatograms of concentrated ethanol 219
extracts of (A) PP and (B) PP + additives
Figure 36. GCxGC-TOF-MS chomatograms of ethanol extracts of 220
(A) HDPE and (B) HDPE + additives
(A) HDPE and (B) HDPE + additives
extracts of (A) HDPE and (B) HDPE + additives
Figure 39. GCxGC-TOF-MS chromatograms of concentrated isooctane 223
extracts of (A) HDPE and (B) HDPE + additives
Figure 40. GCxGC-TOF-MS chromatograms of ethanol extracts of 224
(A) PS and (B) PS + additives
(A) PS and (B) PS + additives
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extracts of (A) PS and (B) PS + additives
extracts of (A) PS and (B) PS + additives
extracts of (A) PET and (B) PET + additives
extracts of (A) PET and (B) PET + additives
extracts of (A) PA and (B) PA + additives
extracts of (A) PA and (B) PA + additives
Figure 48. GCxGC-TOF-MS chromatogram of a concentrated ethanol 232
extract of PP + additives with the additional peaks detected
in the second dimension highlighted
Figure 49. Base peak LC-MS chromatograms of ethanol extracts of PP 233
Figure 50. Base peak LC-MS chromatograms of isooctane extracts of PP 234
Figure 51. Base peak LC-MS chromatograms of ethanol extracts of PS 235
Figure 52. Base peak LC-MS chromatograms of isooctane extracts of PS 236
Figure 53. Base peak LC-MS chromatograms of ethanol extracts of PET 237
Figure 54. Base peak LC-MS chromatograms of isooctane extracts of PET 238
Figure 55. Total ion chromatogram for HDPE and HDPE + additives 239
(isooctane extraction, final solvent acetonitrile) in positive mode
electrospray TOF-MS
(ethanol extraction, final solvent acetonitrile) in positive mode
electrospray TOF-MS
(isooctane extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
(ethanol extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
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Figure 59. Total ion chromatogram for PVC and PVC + additives 243
(isooctane extraction, final solvent acetonitrile) in positive
mode electrospray TOF-MS
(ethanol extraction, final solvent acetonitrile) in positive mode
electrospray TOF-MS
(isooctane extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
(ethanol extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
Figure 63. Total ion chromatogram for PA and PA + additives (isooctane 247
extraction, final solvent acetonitrile) in positive mode electrospray
TOF-MS
Figure 64. Total ion chromatogram for PA and PA + additives (ethanol 248
extraction, final solvent acetonitrile) in positive mode electrospray
TOF-MS
Figure 65. Total ion chromatogram for PA and PA+ additives (isooctane 249
extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
Figure 66. Total ion chromatogram for PA and PA + additives (ethanol 250
extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
Figure 67. Stacked 1H 1D NMR spectroscopy plot of a solvent blank, 251
PP extract and PP + additives extract
Figure 68. Stacked 1H 1D NMR spectroscopy plot of the additives used 252
in the preparation of the PP test materials compared to the
PP extracts and PP + additives extracts
Figure 69. Stacked 1H 1D NMR spectroscopy plot of the additives used in 253
the preparation of the PP test materials compared to the
PP extracts and PP + additives extracts. Highlighted regions
contain resonances from breakdown products or other
impurities
HDPE extract and HDPE + additives extract
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1
Figure 71. Stacked H 1D NMR spectroscopy plot of the additives used 255
in the preparation of the HDPE test materials compared to the
HDPE extracts and HDPE + additives extracts
Figure 72. Stacked 1H 1D NMR spectroscopy plot of the additives used in 256
the preparation of the HDPE test materials compared to the
HDPE extracts and HDPE + additives extracts. Highlighted
regions contain resonances from breakdown products or other
impurities
PS extract and PS + additives extract
in the preparation of the PS test materials compared to the
PS extracts and PS + additives extracts
PET extract and PET + additives extract
in the preparation of the PET test materials compared to the
PET extracts and PET + additives extracts
Figure 77. Stacked 1H 1D NMR spectroscopy plot of the additives 261
used in the preparation of the PET test materials compared
to the PET extracts and PET + additives extracts.
Highlighted regions contain resonances from breakdown
products or other impurities
PVC extract and PVC + additives extract
in the preparation of the PVC test materials compared to the
PVC extracts and PVC + additives extracts
Figure 80. Stacked 1H 1D NMR spectroscopy plot of the PVC + additives 264
extract, the PVC blank extract and the ATBC standard. The
displayed resonances can not be assigned to ATBC and
are hypothesised to be impurities present in the standard.
These impurities are also present in the PVC + additives
sample extract
PA extract and PA + additives extract
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1 1
Figure 82. H– H TOCSY NMR spectrum of the region 5.2 – 1.9 ppm 266
of the CDCl3 extract of the PP + additives extract
Figure 83. 1H– 1H overlaid TOCSY NMR spectra of the region 267
5.2 – 1.9 ppm of the PP without additives extract, pentaerythritol
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
glycerol monostearate, diparamethyldibenzylidene sorbitol
and poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-
alt-1,4-butanedioic acid)
Figure 84. 1H–1H TOCSY NMR spectrum of the region 5.2 – 1.9 ppm 268
of the PP + additives extract. Off-diagonal crosspeaks
correlating the resonances 4.80, 4.52, 4.46 and 3.74 ppm
are highlighted in green, off diagonal crosspeaks from a
hypothesised glycerol monostearate breakdown product
are highlighted in yellow
13
Figure 85. C–1H HSQC NMR spectrum of the region 1H = 5.4 – 3.0 269
13
and C = 80 – 45 ppm of the PP + additives extract
13
Figure 86. C–1H overlaid HSQC NMR spectrum of the region 270
1
H = 5.4 – 3.0 and 13C = 80 – 45 ppm of the PP without
additives extract, pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate), glycerol monostearate,
diparamethyldibenzylidene sorbitol and poly(4-hydroxy-
2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic
acid)
13
Figure 87. C–1H HSQC NMR spectrum of the region 1H = 5.4 – 3.0 271
13
and C = 80 – 45 ppm of the PP + additives extract.
Resonances that are not observed in the overlay spectra
shown in Figure 86 are highlighted in yellow
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ABBREVIATIONS
ATBC Acetyl tributyl citrate

DCHP Dicyclohexyl phthalate
DEHP Di-(2-ethylhexyl) phthalate
DFBP Difluorobiphenyl
DMSO Deuterated methyl sulphoxide
DTBP Ditertbutylphenyl
EI Electron impact
ESBO Epoxidised soya bean oil
FT Fourier transform
GC Gas chromatography
HALS Hindered amine light stabiliser
HCl Hydrogen chloride
HCN Hydrogen cyanide
HDPE High density polyethylene
HIPS High impact polystyrene
HPLC High performance liquid chromatography
HS Headspace
HSQC Heteronuclear single quantum correlation
IR Infra red
LC Liquid chromatography
LDPE Low density polyethylene
NIAS Non-intentionally added substances
NIST National Institute of Standards and Technology
NMR Nuclear magnetic resonance
MFE Molecular feature editor
MS Mass spectrometry
MW Molecular weight
OM Overall migration
OTC Organotin compound
PA Polyamide
PE Polyethylene
PET Polyethylene terephthalate
PP Polypropylene
ppm Parts per million
PS Polystyrene
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ABBREVIATIONS
PTFE Polytetrafluoroethylene
PTV Programmable temperature vapourising
PVC Polyvinyl chloride
SB Styrene-butadiene
SPME Solid phase microextraction
TIC Total ion current
TMS Tetramethylsilane
TNPP Tris(nonylphenyl)phosphite
TOCSY Total correlation spectroscopy
TOF Time of flight
UV Ultra violet
- 20 -
1. INTRODUCTION
1.1 Background
Food packaging materials made of plastics may contain many substances that are not
added intentionally and do not appear in lists of permitted ingredients. These
substances are commonly referred to as NIAS (non-intentionally added substances).
They may be present as impurities in the substances used to make the plastic; as
reaction intermediates formed during the polymerisation processes; or as
decomposition or reaction products formed during polymerisation to make the plastic or
during thermal processing of the plastic to make the packaging. There are two
categories of NIAS. The first, although unintentional, are nevertheless known
substances such as isomers, intermediates and major technical impurities. The
second category is those substances that are undetected or unidentified and so are
unknown. Reaction and breakdown products along with minor impurities often fall into
this second category of unknown NIAS.
It would be fair to say that, to date, regulators and producers have focussed mainly on
substances used intentionally and have largely neglected the NIAS. These substances
should be assessed in accordance with international risk assessment procedures
however it is not really known what is achievable in this area. On the one hand, there
can be extravagant claims that virtually each and every last molecule must be
accounted for. On the other hand, some claim that nothing useful can be achieved and
the issue should be ignored.
In other application areas where polymers are used, impurities, degradation and/or
reaction products play an important role. A lot of polymers contain processing aids
and/or stabilisers in order to maintain the lifetime of the polymer during its use. Due to
various external conditions, e.g. processing and ageing, polymers and additives are
degraded and degradation products will be formed.
Recent examples of the migration of reactions products, are the chlorohydrins and
cyclic reaction products formed from epoxidised soybean oil used as a stabiliser [1],
and semicarbazide formed as a minor decomposition product of azodicarbonamide
used as a blowing (foaming) agent for plastics [2, 3, 4].
1.2 Approach
This project aimed to identify and catalogue the reaction and breakdown products
formed from starting substances used to make six major food contact polymers. A
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combination of theoretical predictions backed-up by advanced separation science and
spectroscopic studies was used. The significance of the findings has been checked by
mathematical modelling of possible migration levels. In this way, the project took a
lead in the analytical aspects of risk assessment of reaction products and breakdown
products of the most commonly used food contact plastics. The objective was to
inform the Food Standards Agency about the principles, practicalities and likely
outcome of the assessment of this class of substances. Thereby, guiding the
development of policy and setting a standard against which the 'due dilligence'
activities of the responsible industries can be judged.
1.3 Objectives
The objectives agreed with the Food Standards Agency for this project were:
Objective 01. Finalise the selection of test polymers with the Food Standards
Agency.
Objective 02. Obtain the test samples along with their formulation details and a
description of the manufacturing process used
Objective 03. Prepare database of ingredients and similes
Objective 04. Conduct a literature search for actual or likely reactions of the
ingredients and their similes, alone or in combination, under the
manufacturing conditions used.
Objective 05. Propose theoretical list for possible impurities/degradation/reaction
products
Objective 06. Prepare extracts of the test plastics
Objective 07. Analyse the extracts for the predicted substances.
Objective 08. Examine and interpret the data for any non-predicted substances
Objective 09. Draw conclusions and prepare final report
2. MANUFACTURE OF THE TEST POLYMERS

2.1 Selection of the polymer types
Six plastics were selected and agreed with the Food Standards Agency. They were:
1. Polypropylene – a general purpose grade
2. Polyethylene – high density
3. Polystyrene – copolymer
4. Polyethylene terephthalate – light stabilised
5. Polyvinyl chloride – plasticised
6. Polyamide – nylon 6,6
- 22 -
These include the five volume polymers used in packaging; polypropylene (PP),
polyethylene (PE), polystyrene (PS), polyethylene terephthalate (PET) and polyvinyl
chloride (PVC) [5]. Briefly, polypropylene is used in films such as confectionery
wrappers and containers including microwavable containers, margarine tubs and
yoghurt pots. High density polyethylene (HDPE) is used in applications such as
containers, milk bottles, food bags, cereal box liners and wrapping films. Polystyrene
finds use in containers such as trays and tubs such as yoghurt pots, in crystal or
foamed forms. PET is used in bottles, high-barrier films and containers used for
ovenable applications. PVC is used in rigid or plasticised forms, in trays, bottles, films
(cling film) and sealing gaskets. The sixth plastic selected was the polyamide (PA)
nylon, which was included in this study because although it is used in lesser volumes, it
finds important and demanding applications by virtue of its good barrier properties and
high temperature resistance. It is also the only one of the six polymers which has a
high content of nitrogen built-into the polymer chain and so its inclusion is interesting
from a reaction/chemistry standpoint. Nylon is used for boil-in-the-bag applications,
sausage casing and kitchen utensils.
2.2 Selection of the test additives

2.2.1 Polypropylene
Although polymerisation conditions and catalysts largely determine the characteristics
of the PP produced, additives must be used to provide the physical properties required
for food packaging applications. These additives include:
• Nucleating agents which improve the clarity and stiffness of the plastic.
Nucleating agents for polypropylene are added at concentrations up to 0.5%.
• Antioxidants which are needed to prevent degradation of the polymer and are
added singly or in combination at 0.01%–0.5%.
• Slip agents which are added for PP films, to reduce friction and blocking - film
layers sticking together. These additives are intended to “bloom” to the film
surface so as to exert their effect.
• Fillers, colours and anti-static agents which are added for particular
applications. As with anti-slip agents, anti-statics are intended to be relatively
incompatible with the polymer and so concentrate at the surface to have
maximum technical effect.
• A carrier solvent which may be used to incorporate these additives into the
polymer, although frequently a concentrate (masterbatch) is made by dispersion
of the additives in the same or similar polymer type.
- 23 -
2.2.2 High density polyethylene
The characteristics of polyethylene can to a large extent be tailored at the
polymerisation stage. But additives are needed for particular food packaging
applications. The additives used to provide the desired characteristics for food contact
applications are:
• Antioxidants which are necessary to prevent the oxidative degradation of the
polymer and are added at 0.01 to 0.5 %.
• Slip agents which are added for PE films, to reduce the film-to-film friction as
well as that between the film and other surfaces with which it comes into
contact. These additives are intended to “bloom” to the film surface to exert
their effect.
• Inorganic colourants which are used to produce white plastics and also can
improve stiffness, printability and gas/vapour permeability.
• Antistatic agents which are incorporated at 0.1 to 0.5% and have limited
solubility in the polymer so that they migrate to the surface and exert their
action.
• Lubricants which are added to assist in film manufacture and injection moulding
operations, used at 0.05 to 0.15%.
• Optical brighteners which are added to brighten colours and to mask the natural
yellowing of the polymer, used at 0.0005 to 0.1%.
2.2.3 Polystyrene
Unlike PP and PE which are almost exclusively made by gas-phase processes, PS
polymers are made in the condensed phase and require carrier solvents, surfactants
and emulsifiers. Residues of these polymerisation aids along with additives used, may
be found in the plastic materials. Other co-monomers are used too, to provide impact-
resistant grades (e.g. HIPS – high impact PS). Additives used in polystyrene plastics
include:
• Antioxidants which are used at concentrations of 0.1 to 1%.
• Processing aids and flow promoters, such as white mineral oils, which are used
at 0.5 to 6%.
• Mould release agents which are used at 0.05% to 2% and are intended to
concentrate to the plastic surface.
• Colourants.
- 24 -
• Emulsifiers which act as surface-active substance used to facilitate the
dispersion of an immiscible liquid compounding material in another liquid and to
stabilise the emulsion thereby produced.
• UV absorbers which act by absorbing harmful ultraviolet radiation and
dissipating it as thermal energy.
2.2.4 Polyethylene terephthalate

The desired properties for packaging applications are attained from the intrinsic
properties of PET polymers. Therefore additives such as antioxidants, plasticisers,
heat- or UV stabilisers are generally not required. Additives that may be used in PET
plastics include:
• Colourants which in low concentrations (usually less than 0.0005%) are used
for some PET grades.
• UV stabilisers which are added for some markets.
• Proprietary acetaldehyde scavengers may be used in PET bottles for
susceptible beverages such as mineral waters.
2.2.5 Polyvinyl chloride

Like PS, PVC polymers are made in the condensed phase and require carrier classes
of compounds such as solvents and emulsifiers as polymerisation aids. A wide range
of additives is also used in PVC compositions. The nature of PVC allows a much
higher incorporation of additives than can be attained with other polymers. Hence the
composition of PVC can range from rigid applications such as bottles to very soft
elastic cap seals. The main additives that can be incorporated in PVC for use in typical
food packaging applications include:
• Stabilisers which are an essential ingredient in any PVC, to protect the PVC
during the thermal processing stages and in use.
• Impact modifiers which are used to provide shock- and crack-resistance to rigid
grades of PVC.
• Plasticisers which are incorporated to achieve flexibility in PVC. They are oil-
like liquids used up to 30% in the PVC.
• Lubricants which are used to aid processing and fabrication operations.
• Colourants which are mainly dispersible pigments solids rather than soluble
dyes.
- 25 -
• Emulsifiers which act as surface-active substance used to facilitate the
dispersion of an immiscible liquid compounding material in another liquid and to
stabilise the emulsion thereby produced.
2.2.6 Polyamide
Like PET, polyamides are condensation polymers. The most important monomers are
caprolactam and laurolactam. Other amine or acid monomers can be copolymerised to
vary the physical properties of the plastic. Additives used are rather few and include:
• Mineral fillers which are used to enhance strength, including glass fibres, talc.
• Mould release agents which are used for when articles such as kitchen tools
are fabricated.
The specific additives selected to fulfil these criteria in each of the test polymers are
given in Tables 1 to 6 along with the level at which they were incorporated into the
plastic and purity information where it is available. Synonyms, CAS numbers,
molecular weights, compound classifications, structures and any current (April 2007)
European legislative restrictions for these additives are described in Appendix 1.
These additives were chosen to be representative of those typically used in plastic
materials and articles intended for contact with food. The levels of each of the
additives included in the plastics are within or close to the ranges described in the
literature. However, it must be appreciated that there are hundreds of different plastic
formulations and manufacturing conditions. The intention was for the project to take
the lead in the analytical chemistry aspects of risk assessment of reaction products and
breakdown products of some, but not all, of the most commonly used food contact
materials.
2.3 Manufacturing conditions of the test polymers

All base polymers were described as food grade and could be used for moulding into
plates. No information was available with respect to the presence of any additives in
these base polymers.
2.3.1 Compounding
Compounding of the polymers with additives by co-extrusion was carried out by
Colorex B.V., Helmond, Netherlands. The temperatures used to compound the base
polymers with the additives were:
PP 180°C
HDPE 180°C
- 26 -
PS 220°C
PET 260°C
PA 280°C
PVC could not be compounded in this way due to the high amount of ‘liquid’ additives.
2.3.2 Moulding
Moulding of the compounded materials into plates was carried out by TNO, Eindhoven,
Netherlands. For PP, HDPE, PS, PET and PA virgin and compounded granules were
used for injection moulding. A mould of 10 x 10 cm with 2 mm thickness was used.
PET and PA were pre-dried at 120°C for 4 hours and 80°C for 4 hours, respectively.
For each polymer, first the control material (polymer with no additives) was injection
moulded followed by the compounded material (polymer with additives). Injection
moulding conditions for the various samples are shown below.
Temperature (°C)
Sample Rear Centre Front Nozzle Mould
PP control - 220 225 230 30
PP compounded - 220 225 230 30
HDPE control 200 210 215 220 33
HDPE compounded 200 210 215 215 35
PS control 200 210 215 215 35
PS compounded 200 210 215 215 35
PET control 250 260 270 280 32
PET compounded 250 260 270 280 32
PA control 260 280 290 280 75
PA compounded 260 280 290 280 75
The PVC could not be injection moulded while the materials could not be converted
into granules. Hence the PVC was processed into sheets using a rolling mill. These
sheets were pressed into plates with dimensions of 7 x 7 cm, 2 mm thickness.
Conditions of the rolling mill and press are shown below.
- 27 -
Rolling mill conditions used for PVC
Split 0.45 mm
Rotation speed roll 1 20.2 rpm
Rotation speed roll 2 16.2 rpm
Temperature (virgin) 195°C
Temperature (compound) 130°C
Press conditions used for PVC
Pre-heating time 4 minutes

Press time 1 minute
Temperature (virgin) 195°C
Temperature (compound) 140°C
Once cooled the plates were overwrapped in aluminum foil and distributed to the
analytical laboratories of TNO and CSL.
3. IMPURITIES, REACTION PRODUCTS AND BREAKDOWN PRODUCTS OF

THE SELECTED PLASTICS AND ADDITIVES
3.1 Polypropylene
3.1.1 General aspects of polypropylene chemistry
PP is composed of linear hydrocarbon chains and therefore its properties quite closely
resemble those of PE. Homopolymer PP is one of the lightest thermoplastics with a
density of ~0.9 g/cm3. The high crystallinity gives PP its desirable characteristics. The
melting temperature of commercial materials is around 160-170°C, higher than that of
PE. The tertiary C atoms reduce the chemical inertness of PP and make PP more
sensitive to oxidation. This sensitivity towards oxidation must be countered by using
antioxidants. PP possesses good water vapour barrier and fat resistance properties.
Normal PP films have limited food packaging applications because of their low cold
temperature resistance. Copolymer mixtures with ethylene are used to improve cold
resistance, heat sealability, material strength and seal strength. The use of sorbitol
based nucleating agents enables the fabrication of clear PP product. PP is an
excellent material for injection and extrusion processes.
The thermal oxidation of PP is well studied. However, the initiation step is the least
understood and is still a matter of discussion. During polymer processing, mechanical
stresses and/or heat may lead to the formation of macroalkyl radicals through
- 28 -
homolysis of carbon-hydrogen or carbon-carbon bonds. The direct interaction of PP
with oxygen or catalyst residues may also contribute to the formation of free radicals.
In the presence of oxygen the carbon-centred radicals formed yield hydroperoxides.
There is strong evidence that after processing, PP generally contains hydroperoxide
groups. It is very likely that they are of great importance for the oxidative degradation
of PP. The chain propagation, chain-branching and chain termination steps are rather
straightforward [6]. The chemical changes as a result of thermal oxidation of PP
consist mainly in the formation of aldehydes, ketones, carboxylic acids, esters and
γ-lactones.
Photooxidation of commercial PP is probably promoted by minute traces of catalyst

residues, hydrogen peroxide, carbonyl groups or double bonds. These impurities are
believed to be formed by thermal oxidation during polymer manufacturing, processing
or storage. Isolated hydroperoxide groups and sequences of hydroperoxide groups are
formed in intermolecular and intramolecular oxidation steps [7]. The alkoxy radicals
resulting from the photolysis of hydroperoxides do not only abstract hydrogen as do the
alkylperoxy radicals but may also undergo decomposition reactions resulting in polymer
chain scission. β-scission has been considered as the main reaction responsible for
the decrease in molecular weight of PP. Ketones are regarded as primary
photooxidation products resulting from the bimolecular chain termination between
secondary peroxy radicals. Resulting degradation or decomposition products are acids
and ketones [8].
A few studies have dealt with polyolefins exposed to electron beam radiation [9].
Generally this results in much more complex degradation mechanisms and thus
different degradation products compared to standard processing conditions or outdoor
exposure. This is because the dose rate is higher giving a higher flux (concentration)
of radical species.
3.1.2 Diparamethylenedibenzylidene sorbitol

Diparamethylenedibenzylidene sorbitol and derivatives are all-organic nucleating
agents particularly suitable for PP. These nucleating agents form structures in the
polymer melt which cause the formation of a large number of very small crystallites in
the polymeric organic material [10]. The nucleating agents are usually added before
processing and act especially on cooling of the polymer melt. A moulding produced in
this way shows significantly better transparency, hardness, impact resistance and
modulus of elasticity.
- 29 -
A significant problem of diparamethylenedibenzylidene sorbitol or derivatives is partial
decomposition that can take place before, during or after processing. Partial
decomposition occurs especially during processing at high temperatures (> 200°C)
[11]. In addition, the hydrolysis of the acetalic structure, which is fairly labile
chemically, has been blamed for partial cleavage of the diparamethylenedibenzylidene
derivatives. This instability is exhibited in particular by odiferous problems and by a
reduction in effectiveness under some conditions of use. Thermal treatment may
generate, encourage or amplify decomposition phenomena, in particular hydrolysis
and/or sublimation of the alditol acetal and the emission of undesirable odours, in
particular of an aldehyde type [12]. Possible hydrolysis products are acetaldehyde,
3,4-dimethyl-benzaldehyde and sorbitol.
3.1.3 Tris(2,4-di-tert-butylphenyl)phosphite
Organic compounds of trivalent phosphorus are excellent processing stabilisers for
polyolefins. They are often used in combination with phenolic antioxidants and reduce
the consumption of these phenolic antioxidants during processing. These stabilisers
act as hydroperoxide-decomposing antioxidants and also complex with and block
polyvalent metal ions that otherwise cause chain initiation.
For aromatic phosphites, like tris(2,4-di-tert-butylphenyl)phosphite, the reaction with

hydroperoxides leads to the formation of alcohols and the corresponding phosphates,
i.e. oxidised tris(2,4-di-tert-butylphenyl)phosphite. Oxidised tris(2,4-di-tert-
butylphenyl)phosphite is often found in (migration) extracts of polymers containing
tris(2,4-di-tert-butylphenyl)phosphite and in EU legislation (Directive 2002/72/EC, as
amended) the migration of tris(2,4-di-tert-butylphenyl)phosphite in food (simulants)
should be calculated as a total specific migration limit (SML(T)) by adding the amounts
of tris(2,4-di-tert-butylphenyl)phosphite and oxidised tris(2,4-di-tert-
butylphenyl)phosphite.
Another very common degradation product of tris(2,4-di-tert-butylphenyl)phosphite is

2,4-di-tert-butylphenol [13,14]. This compound can be formed by hydrolysis of the
phosphate leading to 2,4-di-tert-butylphenol and di(2,4-di-tert-butylphenyl)phosphate.
This reaction can be repeated, ultimately leading to the formation of phosphoric acid
[15]. Various phosphate species have been identified in polyolefin films containing
tris(2,4-di-tert-butylphenyl)phosphite after long-term exposure to biotic and abiotic
conditions [13].
- 30 -
Various studies have focused on the formation (and migration) of degradation products
in polyolefin films as a result of γ-irradiation/e-beam [16-19]. Degradation products that
could be identified were 2,4-di-tert-butylphenol, 1,3-di-tertbutylbenzene and oxidised
tris(2,4-di-tert-butylphenyl)phosphite.
Pyrolysis GC-MS has been a valuable tool to investigate the ‘weak’ points in the
structure of antioxidants [20]. Although the degradation takes place in the absence of
oxygen, some of the pyrolysis products formed are expected to be very similar to
degradation products observed under real-life degradation conditions. For tris(2,4-di-
tert-butylphenyl)phosphite, the hindered phenol unit produces two sets of pyrolysates,
one set contains alkyl-substituted benzenes and the other set contains alkyl-substituted
phenols [20]. However, it should be stressed that pyrolysis is carried out at
temperatures higher than those reached during processing and as a result the number
and concentration of degradation products formed during processing are expected to
be much lower.
3.1.4 Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)

Hindered phenols protect plastics against thermal oxidation, especially during
processing and long-term storage/use of polyolefins. Although they can be used as
single stabilisers, they are significantly more effective when combined with e.g. organic
compounds of trivalent phosphorous, i.e. tris(2,4-di-tert-butylphenyl)phosphite, UV
absorbers or hindered-amine light stabilisers (HALS) compounds. Especially the
combination of pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) with
tris(2,4-di-tert-butylphenyl)phosphite is often applied in polyolefins in which the
phosphite is used as a processing, i.e. short-term, stabiliser which reduces the
consumption of pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)
during melt processing. As a result pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate) is much more effective in the final product.
A variety of antioxidants have been used to inhibit degradation of thermally sensitive

polymers, like polyolefins, during their life-time. Low-molecular weight antioxidants, i.e.
butylated hydroxytoluene, are preferred during processing where it must be capable of
freely diffusing through the polymer towards the initiation sites generated during
processing. On the other hand for long-term protection large antioxidants, like
pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), are preferred which
are less mobile and less volatile and thus have superior retention in the polymer.
- 31 -
Hindered phenolic antioxidants break free-radical chain reactions by hydrogen transfer
from the phenolic hydroxyl group to alkylperoxyl groups derived from polymer oxidation
[21,22]. The resulting phenoxy radical is resonance stabilised and so the radical chain
reaction is stopped. The phenoxyl radical intermediates are precursors of all isolated
transformation products of phenolic antioxidants [21-23]. Phenoxyl radicals participate
in disproportionation reactions, autorecombination and recombination with
alkylperoxyls. Alkylperoxycyclohexadienones arise from the cyclohexadienyl radicals
and alkylperoxyls ROO·. During weathering, phenolic antioxidants are photooxidised
into hydroxyperoxycyclohexadienones.
Hindered phenoxyls containing at least one hydrogen atom on the carbon atom in
position four, like pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
disproportionate to the parent phenol and a relevant quinone methide. The latter
species are the stable transformation products of phenolic antioxidants.
In several studies degradation products of hindered phenol-type antioxidants have

been analysed. Several degradation products have been detected as migrants from
polyolefins, i.e. 2,6-di-tert-butyl-benzoquinone, 7,6-di-tert-butyl-1-oxaspiro[4.5]deca-
6,9-diene-2,8-dione [24]. Haider and Karlsson [13] have studied loss- and
transformation products of aromatic antioxidants in PE film under long-term exposure
to biotic and abiotic conditions (UV radiation, air, compost, water). For pentaerythritol
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) transformation of the phenoxy
radical of the pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)
produced ester, acid, dealkylated cinnamate and quinine products. Studies on the
identification of additives and degradation products of additives from polyethylene
pipelines into drinking water by GC-MS showed that most compounds could be
assigned to bis-tert-butylphenol-like compounds [25].
Low mass oligomers and polymer additives from polyolefins were determined using
soxhlet extracts and capillary supercritical fluid chromatography [26]. PP extracts
showed the presence of pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate) and dioctadecyl-3,3’-thiodipropionate. In PE extracts various
degradation products of pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate)/butylated hydroxytoluene could be identified by GC-MS,
including di-tert-butyl-benzene, di-tert-butylphenol, di-tert-butyl-benzoquinone, di-tert-
butyl-benzyl-methyl-propanoate and di-tert-butyl-quinonemethidepropionic acid.
- 32 -
Studies on hindered phenolic antioxidants (in packaging) after e-beam treatment
revealed similar transformation products [9,16,17].
Using pyrolysis GC-MS [20] on pentaerythritol tetrakis(3,5-di-tert-butyl-4-

hydroxyhydrocinnamate), all pyrolysates originate from the side chain fragmentation of
the hindered phenol unit. The pyrogram of pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate) can almost be viewed as the pyrogram of hindered phenol
(3,5-di-tert-butyl-4-hydroxycinnamate) unit.
3.1.5 Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetra
methyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-
piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] is another
polymeric HALS compound commonly used in plastic food contact materials, especially
polyolefins. The loss of the title substance from LDPE and the identification of
degradation products of additives after exposure to water, air and compost were
studied by GC-MS [27] where the major degradation product was 2,2,6,6-tetramethyl-4-
piperidine.
Due to the relative high molecular weight of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-

1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-
[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] and therefore its incompatibility with both GC-
MS and LC-MS, pyrolysis GC-MS or reactive thermal desorption GC have been used
to analyse polymers containing it. For example, Kimura et al. [28] used reactive
thermal desorption GC to identify the substance in PP samples. However, these
analytical techniques have not been used for degradation studies but mainly for
identification purposes. Blaszo [29] studied the thermal decomposition of two
polymeric HALS at various temperatures. Various possible thermal degradation
products and mechanisms for HALS stabilisers were identified. Although the
temperatures are significantly higher than during processing and use, it shows where
the weak points in the structure are and which degradation products may be expected.
Typical pyrolysis products were aza-2,2,6,6-tetramethyl-3-cyclohexene, 2-methyl-3,5-
pentadiene, tert-octene, isopropenylamine, 2,6-dimethylanilines, 2,6-dimethylpyridine
and 1,3-dimethylbenzene.
- 33 -
3.1.6 Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic
acid)
Hindered amines are a well known category of photostabilisers used to protect
polymers, especially polyolefins, against UV degradation. The mechanism by which
these HALS protect against photodegradation is complex and has not yet been
completely established. It has been proposed that HALS compounds react with
hydroperoxides, formed in the polymer, to yield stable nitroxyl radicals. These radicals
are very effective in scavenging alkyl or macroalkyl radicals, thereby forming
hydroxylamines [30].
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) is a

polymeric HALS compound used often in polyolefin food contact materials. Very often
it is combined with another polymeric HALS compound, i.e. poly[[6-[(1,1,3,3-
tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]
-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]. Poly(4-hydroxy-2,2,6,6-
tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) oligomers contain 2,2,6,6-
tetramethylpiperidine moieties bound at the fourth carbon atom to the macromolecule.
Furthermore ester bonds of dicarboxylic acid and a 4-hydroxypiperidine are typical for
such compounds.
The structure of poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-

butanedioic acid) contains ester carbonyl and piperidinyl groups in the backbone. The
former can be photolysed by the Norrish reaction while the latter can be oxidised to the
nitroxyl radical. Both reactions can break the polymer chain and decrease the
effectiveness of this additive. Photolysis was observed for poly(4-hydroxy-2,2,6,6-
tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) after irradiation. With Fourier
transform-infra red (FT-IR) a decrease in methyl groups and esters was observed while
infra red absorbances attributed to hydroxyl, carboxyl, carboxylate and double bond
groups increased [31].
No specific literature was found on possible degradation products of poly(4-hydroxy-

2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) in polymers during
processing or use. Some clues on possible degradation products of poly(4-hydroxy-
2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid), especially due to
thermal treatment, were given by pyrolysis GC-MS analysis of pure poly(4-hydroxy-
2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) [28,29]. Typical
pyrolysis products were aza-2,2,6,6-tetramethyl-3-cyclohexene, 2,6-dimethyl-2,4,6-
- 34 -
heptatriene, 2-methyl-3,5-pentadiene, butanedioic anhydride, 1-aza-2,2,6,6-
tetramethyl-3-cyclohexeneethanol and methyl-1-aza-2,2,6,6-tetramethyl-3-
cyclohexeneethyl succinate.
3.1.7 Erucamide
For certain applications, it is desirable for plastic surfaces to have good slip properties.
Certain additives migrate strongly to the surface and a uniform invisibly thin coating is
formed. These slip agents are important in the production of polyolefin films. They
ensure good handling properties, particularly on automatic packaging machines.
Erucamide or closely related fatty acid amides are normally used in PP.
Thermal degradation which occurs during film processing is known to have an adverse
effect on the properties of slip agents. This can cause slip additives to become
ineffective, especially for slip additives with low thermal stability. Odorous and
coloured compounds are amongst the products that are formed from the degradation of
slip additives [32-34]. Highly coloured fatty acid nitriles have been isolated as by-
products during the synthesis and isolation of fatty acid amides [32,33]. These nitriles
are formed by dehydration of fatty acid amides. For erucamide this leads to erucyl
nitrile (T> 200°C) which can hydrolyse to erucic ac id [35]. A degradation product of
erucamide that was identified by GC-MS was nonanal. The proposed degradation
mechanism of erucamide suggested the possible formation of 13-oxo-tridecanoic acid,
nonanal and 13-hydroxy-cis-14-docosenamide [36].
3.1.8 Glycerol monostearate

Glycerol monostearate is a non-ionic surfactant used as external lubricant for plastics.
In general glycerol monostearate has a purity of >90%. Glycerol monostearate is
synthesised by reaction of triglycerides with an excess of glycerol [37]. Therefore the
impurities are mainly diglycerides, unreacted triglycerides, glycerol and fatty acids
(i.e. stearic acid, tetradecanoic acid, hexadecanoic acid) and their esters. If the
triglyceride is sourced from edible fats or oils it may have impurities from them.
No literature was found on the degradation of glycerol monostearate during processing

and use in polymers. Hydrolysis would form stearic acid and glycerol.
3.1.9 Calcium carbonate

Naturally occurring calcium carbonates are sedimentary rocks of marine origin.
Calcium carbonates in the form of ground chalk, limestone or marble for use in
- 35 -
thermoplastics should possess certain properties including some limits of impurities like
magnesium carbonate and iron oxide. The same accounts for synthetic precipitated
calcium carbonates. Impurities in calcium carbonates will be mainly of inorganic origin.
Calcium carbonates, used as fillers in food contact plastics, are stable under normal
processing conditions and during use. At high temperature or under acidic conditions
they can release carbon dioxide and form calcium oxide/hydroxide.
3.2 High density polyethylene

3.2.1 General aspects of polyethylene chemistry
HDPE is defined by a density of greater or equal to 0.941 g/cm3. HDPE has a low
degree of branching and thus stronger intermolecular forces and tensile strength. It
can be produced by chromium/silica catalysts, Ziegler-Natta catalysts or metallocene
catalysts. The lack of branching is ensured by an appropriate choice of catalyst.
HDPE will age as a result of exposure to light, oxygen and heat which results in a loss
of strength, discolouration and a decrease in the glossiness of the product.
Antioxidants are added, along with other additives, to reduce these ageing effects.
Due to a high friction coefficient polyolefin films tend to stick to themselves or to the
equipment used in their production. The addition of a slip-agent modifies the surface
properties of the polymer and reduces the film to film friction, for example on the roll,
and the friction between the film and other surfaces with which it comes into contact.
Anti-static agents are added to reduce surface resistance and hence dissipate high
electrical charge densities on the surface of the plastics. Both slip-agents and anti-
static agents are intentionally incompatible with the polymer and as a result they bloom
to the surface where they are able to impart their desired effects. Inorganic pigments
are added to impart colour to the polymer. UV absorbers act by absorbing the harmful
UV radiation so that it does not lead to polymer degradation.
Microwave-assisted extraction was used in a comparison of virgin and recycled films

from mixed solid waste [38]. GC-MS was then used to identify components of the
films. The recycled films had been in contact with foodstuffs so most of the compounds
extracted were fragrance and flavour constituents, for example alcohols, esters and
ketones. In the virgin material the majority of compounds determined could be grouped
into the following categories: aliphatic hydrocarbons, branched alkanes, branched
alkenes and ketones. A full list is provided in Table 7 and these compounds were also
detected in the recycled HDPE in similar concentrations. Aromatic hydrocarbons were
also detected and it was proposed that these are breakdown products from the polymer
- 36 -
additives. Concern was raised over the presence of ethylbenzene and xylenes, but
estimates suggested that their concentrations were quite low.
3.2.2 Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite is a phosphonite
processing stabiliser. It acts as a secondary antioxidant reacting with hydroperoxides
formed during polymer processing thereby leaving the primary antioxidant (in this
example the octadecyl 3,3-di-t-butyl-4-hydroxyhydrocinnamate) free to act throughout
the life of the polymer. It is also reported to prevent discolouration of the polymer.
No details of any impurities, reaction products and degradation products of tetrakis(2,4-

di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite in polymers could be found
documented in the scientific literature. However, considering the structure and known
chemistry of phosphonite compounds a number of reaction and breakdown products
can be predicted. It’s stability in food simulants was investigated by Franz et al. [39].
The authors report that a mixture of at least seven constituents were detected when a
polymer containing the phosphonite was exposed to ethanolic and acetic acid
simulants. The product information sheet for the stabiliser states that it may contain
low levels of impurities such as chlorides and advises that appropriate amounts of an
acid acceptor are also used in the polymer formulation.
3.2.3 Octadecyl 3,3-di-t-butyl-4-hydroxyhydrocinnamate

Octadecyl 3,3-di-t-butyl-4-hydroxyhydrocinnamate is a sterically hindered phenolic
antioxidant that protects the substrate against thermo-oxidative degradation. Much of
the chemistry described for pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate) in Section 3.1.4 is also of relevance here.
31
HPLC-UV, HPLC-NMR, supercritical fluid chromatography, fluorimetry, GC-MS and P
NMR spectroscopy were used to characterise the degradation products of common PE
processing stabilisers and antioxidants [40]. The phosphite stabilisers were seen to
either oxidise to phosphate species or hydrolyse to phosphonate species under
processing conditions. These oxidation products has been reported elsewhere [41,42].
The oxidation of octadecyl 3,3-di-t-butyl-4-hydroxyhydrocinnamate yields a quinone
methide and a cinnamate, which can be converted into dimeric species, that can be
either conjugated or not. Again the presence of these compounds has been reported
elsewhere [43]. Under thermal degradation conditions (1 day at 180oC) the major
product was identified as the cinnamate, whilst degradation (250oC) in the presence of
- 37 -
air afforded mono- and di-alkylated derivatives of octadecyl 3,3-di-t-butyl-4-
hydroxyhydrocinnamate. A retro-Friedel-Crafts reaction was also seen to take place
(at 250oC) and isobutylene was liberated.
PP and PE plastics can be exposed to ionising radiation during sterilisation processes

and as a consequence degradation products can migrate into the surrounding media.
Specific migration studies have shown that concentrations of stabilisers such as
octadecyl 3,3-di-t-butyl-4-hydroxyhydrocinnamate and tris(2,4-di-tert-
butylphenyl)phosphite decreased upon irradiation yet overall migration increased,
suggesting the formation of degradation products, although identification of these was
not attempted [44]. Since overall migration from polyolefins is normally dominated by
oligomeric hydrocarbon species, it can be expected that the raised OM was caused by
polymer degradation to a lower molecular weight distribution. A study of plastic food
packaging materials, including PE plastics exposed to gamma radiation, showed
degradation products of hindered phenol antioxidants which correspond to those seen
in other labs not using radiation [45]. The oxidation products of the phosphite additives
were the corresponding phosphate species and other products were identified as
2,4-tert-dibutyl phenol and 2,6-di-tert-butyl-1,4-benzoquinone, presumably from tris(2,4-
di-tert-butylphenyl)phosphite. Degradation products attributed to octadecyl 3,3-di-t-
butyl-4-hydroxyhydrocinnamate were the de-butylated analogue and a range of
oxidation products including the cinnamate ester and dimeric species.
3.2.4 Oleamide
Given that oleamide is structurally similar to erucamide (C18 versus C22) it is expected
that the same types of reaction and breakdown products will form. The discussion is
not repeated here (see Section 3.1.7).
3.2.5 Titanium dioxide

Work has been carried out into the effect of the grade and type of titanium dioxide in
PE polymers on oxidative and thermooxidative degradation [46-51]. FT-IR was used to
follow the degradation of the polymer, using the formation of a carbonyl band as
evidence of degradation. This is formed from a hyperperoxide due to the action of the
titanium dioxide upon the PE backbone.
Titanium dioxide itself is considered to be inert however it may influence the rate of
oxidation of the polymer and other additives. Titanium dioxide pigment has a small
particle size and a large surface area and this surface may promote chemical reactions
- 38 -
such as (photo)oxidation as described above. Also, commercial grades of TiO2 are
frequently surface-treated to improve the compatibility of the inorganic pigment with the
organic polymer into which it has to be incorporated. These surface treatments can be
organic or inorganic or a combination of both. Their exact nature is proprietary.
3.2.6 N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine
No specific literature was found on possible degradation products of N,N-bis-(2-
hydroxyethyl)alkyl(C13-C15)amine in polymers during processing or use. From the
structure it may be expected that thermolysis could yield the corresponding C13-C15
amines and ethylene oxide and hydrolysis could yield the amines plus 1,2-ethane diol.
3.2.7 Glycerol monooleate

Glycerol monooleate is widely used as a non-ionic surfactant and emulsifier. It is
synthesised by reaction of glycerine and oleic acid. No literature was found on the
degradation of glycerol monooleate during processing and use in polymers. Hydrolysis
will result in the formation of oleic acid and glycerol. Oxidation of the double bond
would yield the normal oxidation products of monounsaturated fatty acids.
3.2.8 Sodium (C10-C18) alkyl sulfonate

No specific literature was found on possible degradation products of sodium (C10-C18)
alkyl sulfonate in polymers during processing or use. From the structure it may be
expected that hydrolysis will yield the corresponding sulfonic acids.
3.2.9 2,5-Bis(5’-tert-butylbenzoxazol-2-yl)thiophene
No specific literature was found on possible degradation products of 2,5-bis(5’-tert-
butylbenzoxazol-2-yl)thiophene in polymers during processing or use.
3.3 Polystyrene
3.3.1 General aspects of polystyrene chemistry
As a thermoplastic PS can be processed between temperatures of 150-300°C.
Thermal depolymerisation takes place by splitting out the styrene and as a
consequence commercial grades do not normally contain less than 200 mg/kg styrene
because unzipping to form styrene can occur even after vacuum-stripping. The
impurities in styrene feedstock include toluene and xylenes. Being unreactive -
containing no double-bonds to polymerise - they can accumulate and concentrate in
the polymer. Products formed by PS are hard and transparent with high brilliance and
resistance to many chemicals. Its disadvantages are its brittleness and sensitivity to
- 39 -
stress cracking. Because of its high permeability to gases and vapours it is mainly
used as a material for products requiring short shelf lives, usually refrigerated and not
having too high a fat content. Through polymerisation of a styrene rubber solution one
obtains styrene-butadiene (SB) polymer. Packaging for food as well as household
appliances and containers like drinking cups and disposable dishes are all made from
PS and SB. Because of its properties it is also known as HIPS.
Reprocessing of polystyrene, i.e. repeated extrusion at 190°C, induces changes in the

mechanical and thermal properties as well as in the average molecular weight [52].
The latter will result in an increase in (low mass) oligomers although the extrusion
process affects essentially the high macromolecules chains of polystyrene [52].
In another study multiple processing and accelerated ageing were employed to model
the processing, recycling and service life of HIPS. The oxidative stability of HIPS is
affected by both the reprocessing cycles and by thermo-oxidative ageing.
Reprocessing induces heterogeneous changes in the chemical structure of HIPS, with
the formation of oxidative moieties and consumption of part of the unsaturations. The
thermo-oxidative ageing mainly affects the polybutadiene phase in HIPS, with a
reduction of the trans-1,4- functional group and formation of hydroxyl and carboxyl
groups [53]. Thermal oxidation is negligible when PS is processed in the absence of
air. However, complete exclusion of air in commercial processing is seldom achieved.
Thermal degradation of polystyrene has been simulated by pyrolysis GC-MS [54,55].

Thermal fragmentation of styrene-butadiene rubber showed mainly butadiene, styrene,
styrene-oligomers and butadiene-oligomers. Significant mass loss of PS does not take
place at temperatures below 300°C [52].
In the presence of oxygen, UV light leads to yellowing and brittleness. Groups capable
of absorbing UV radiation are formed when air is present, and the polymer is then
sensitised to photooxidation. Hydroperoxides are believed to be the first molecular
products formed, and these then decompose to form ketone groups.
The light-induced degradation of commercial polystyrene is attributed to the scission of

the weak O-O bonds of the peroxide groups that result from the processing.
Abstraction of the tertiary-bonded hydrogen occurs preferentially, leading to the
formation of benzyl-type radicals. These radicals in turn react further to hydroxyl
groups, chain ketones and acetophenone structures.
- 40 -
In styrene-butadiene rubbers, photodegradation starts with the generation of free
radicals by UV light causing reaction of double bonds in the polybutadiene segment.
The initial polybutadiene photooxidation initiates the rapid degradation of polystyrene
and yellowing [56].
Radiolysis products of gamma-irradiated PS were studied by GC and HPLC [57]. The

presence of 1-phenylethanol and an increase of acetophenone, benzaldehyde and
phenol were observed in irradiated PS.
3.3.2 Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate)
No specific information could be found on the degradation of
ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate). However
due to the structural similarity of Irganox-type additives the predicted degradation
products will also be very similar. Therefore, for a general description of transformation
products of Irganox-type additives and its mechanisms see Section 3.1.4. One
significant difference in the title compound is the presence of one methyl group and
only one tert-butyl group instead of two tert-butyl groups. Hence the degradation
products can be expected to include 2-tert-butyl-6-methylphenol instead of 2,6-di-tert-
butylphenol.
3.3.3 Tris(nonylphenyl)phosphite
The same accounts for tris(nonylphenyl)phosphite (TNPP) which shows great structural
similarity with tris(2,4-di-tert-butylphenyl)phosphite. Therefore similar degradation
products can be expected, e.g. tris(nonylphenyl)phosphate, di(nonylphenyl)phosphate
and nonylphenol. TNPP has been used for decades as a stabiliser within styrenic
block copolymers. There are several ongoing reviews on the risk assessment of TNPP
within the EU and the USA. One concern that has been raised is the possible release
of nonylphenol from TNPP by e.g. hydrolysis [58].
3.3.4 Di-(2-ethylhexyl) phthalate

One of the most commonly applied plasticisers in plastic products is di-(2-ethylhexyl)
phthalate (DEHP) although its use in food contact materials is quite limited now.
Various studies have focussed on DEHP and its metabolites, for example in
biodegradation studies [59] and in vitro experiments [60]. Three possible classes of
DEHP metabolites are proposed: i) alcohols derived by hydrolysis reaction, ii) acids
produced by alcohol oxidation, iii) degradation products retaining the phthalic moiety
[60]. Metabolites that could be identified in these studies were 2-ethylhexanoic acid,
- 41 -
2-ethylhexanol, phthalic acid, mono-2-ethylhexyl phthalate [59,60]. These types of
degradation products can also be expected for DEHP used in plastics. A pyrolysis GC-
MS study showed that the main pyrolysates of di(2-ethylhexyloctyl) phthalate are
benzene, octane isomers, 2-ethylhexylaldehyde, 2-ethylhexyl alcohol and DEHP [61].
3.3.5 N,N-Bis(stearoyl)ethylenediamide
No information was found on the degradation of N,N-bis(stearoyl)ethylenediamide used
as additives in plastics. From the chemical structure of
N,N-bis(stearoyl)ethylenediamide the following degradation products can be expected:
octadecanamide, stearic acid and octadecanol.
3.3.6 Polyethylene glycol 4-tert-octyl-phenyl ether, n~5 and polyethylene glycol 4-tert-
octyl-phenyl ether, n=9-10
Polyethylene oxide ethers of octylphenol, i.e. octylphenol ethoxylates, are versatile
non-ionic surfactants. No literature was found on the degradation of octylphenol
ethoxylates used in polymers under processing conditions or usage. However, some
studies were found looking at the biodegradation of these substances [62]. These
studies give some clues on what type of degradation products can be expected when
used in polymers after processing or during use or storage. Above all octylphenol, in
analogy to nonylphenol, can be expected to be a major degradation product.
Furthermore, degradation leads to a shift from high oligomers to low oligomers. In the
case of polyethylene glycol 4-tert-octyl-phenol ether, n = 9-10, the peaks of oligomers
with n = 5 to 15 decrease while the peaks of oligomers with n < 5. The dominant peak
is the one corresponding to n = 3 [62].
3.3.7 2-(2’-Hydroxy-5’-methylphenyl)benzotriazole
Among the UV absorbers for polymers the benzotriazole-type absorbers are in general
the first choice because of their colour stability and low initial colour. One of these
class of UV absorbers is 2-(2’-hydroxy-5’-methylphenyl)benzotriazole. No specific
literature on degradation (products) of 2-(2’-hydroxy-5’-methylphenyl)benzotriazole was
found. However some general information is available on the photochemistry of
benzotriazoles [63,64]. Little or no direct photolysis of benzotriazole UV absorbers in
the absence of oxygen has been observed. A mechanism has been suggested which
includes a radical attack on the phenolic ring resulting in breaking of the aromaticity of
the ring. Further photoreactions lead to the cleavage of the benzotriazole moiety from
the phenolic ring. Benzotriazole was the major product of photolysis.
- 42 -
3.4 Polyethylene terephthalate
3.4.1 General aspects of polyethylene terephthalate chemistry
Linear saturated polyesters are hard, semicrystalline thermoplastics that are impact
resistant even at low temperatures, smooth and have a good wear resistance. The
barrier properties of PET are good with respect to gases, aromas and fats but it has
slightly lower barrier properties against water vapour. Because of its partial crystallinity
PET has a high strength at short-time load. The gas barrier properties can be
improved by coextrusion with a barrier layer such as polyamide. Biaxially stretched
PET covers an important application area of bottles. With improved barrier properties it
can also be used for wine and beer.
PET is part of an important class of polyesters with a wide variety of applications.

Some of the properties that characterise PET are crystallisation upon orientation, high
mechanical strength, high barrier properties, optical clarity and the ability to be recycled
as a thermoplastic polymer. PET undergoes several types of degradation under
different conditions. With the absence of light, reactive ions and chemical reagents, the
considered degradation types in the processing of PET are thermal, thermal-oxidative
and hydrolytic degradation. Heat (from elevated temperatures), oxygen (from the
environment) and water (from the atmosphere) are the main causes of the reduction in
molecular weight and the formation of carboxyl end-groups. The contribution of the
different types of degradation to the overall molecular weight loss depends on the
processing conditions.
Hydrolysis of PET is considered to be a random chain-scission reaction. The result of

hydrolytic degradation is therefore the formation of a carboxyl and hydroxyl end-group
for the reaction of each water molecule with a PET unit. Hydrolysis is a rapid reaction
but it does not reach 100% completion in the processing stage. The rate of hydrolysis
is directly proportional to two components: carboxyl end-group concentration and water
concentration. Hydrolytic degradation results in the formation of carboxyl end-groups
which increase the rate of hydrolysis due to an autocatalytic mechanism. The
molecular weight decreases exponentially with increased resin moisture content [65].
Thermal degradation takes place mainly during the polycondensation stage due to the
high temperatures (~280-300°C). This is the reason for the relatively low molecular
weight of PET. The mechanism for thermal degradation involves a random alkyl-
oxygen chain scission of the β-hydrogen type. Acetaldehyde, water, carbon dioxide
and carboxyl end groups are the main products of thermal degradation of PET [66].
- 43 -
The degradation of PET in the presence of air proceeds through a free radical
mechanism. A free macroradical is generated by heat, radiation or stress. This reacts
with oxygen to yield a peroxy radical. The peroxy free radical abstracts hydrogen from
another polymer molecule creating a new macroradical and a hydroperoxide. Then the
hydroperoxide decomposes to two new free radicals which are also initiators of the
chain reaction [67]. The thermooxidative degradation takes place mainly during the
product formulation in injection machines or during extrusion of the polymer melt
(moulding). In these procedures there is a critical time period for polymer melt which
cools down and finally solidifies. During this period the polymer can be affected by air
and the results are in general the same as in the case of thermal degradation.
Discoloration is one of the most critical problems that arise during melt processing of
PET. A possible pathway for colour formation in PET is peroxidation of the PET at the
ether link in diethylene glycol incorporated into it. The peroxides break down to give
hydroxyl radicals which attack the terephthalic ring and ultimately lead to quinine-type
structures incorporated into the PET backbone. These compounds have only to be
present in ppm amounts for the PET to be discoloured [68]. Further, the formation of
additional carbonyl functionalities and conjugated chromophoric systems complete the
colour formation process [69].
Not many papers have been published on the photodegradation of PET. Although PET
shows a lifetime significantly longer than polyolefins, exposure to UV light deteriorates
unstabilised PET. Photodegradation leads to chain scission reactions and the
formation of carboxyl end-groups. Samples with an UV absorber showed less
deterioration in tensile properties [70].
PET is often recycled and this recycled PET is more sensitive towards thermal and
hydrolytic degradation compared to virgin PET [71]. Recycling PET gives rise to a
decrease in the melt viscosity, average molecular weight, thermal and mechanical
properties of the material because of hydrolytic chain scission and thermomechanical
degradation undergone during processing [71].
During the degradation process of PET there is a change in functional group

concentration with an increase in carboxyl groups and a decrease in hydroxyl groups.
When all the hydroxyl end groups are removed, anhydride formation occurs. Benzoic
acid and vinyl benzoate could be produced from a simple repeat segment. In addition,
vinyl benzoate may decompose further to yield benzoic acid and acetophenone. Other
- 44 -
substances can also be produced as terephthalic acids, acetaldehyde, acid anhydrides,
benzene, ethylene dibenzoate, acetylene, and carbon monoxide and dioxide through
decomposition of the repeat unit in the chain (2-benzoyloxyethyl terephthalate).
Degradation occurs primarily via scission of the main chain in random manner to yield
carboxyl end groups and a vinyl product which can combine to form an ethylidene
product which decomposes further [72].
The formation of acetaldehyde has attained a lot of attention. Shukla et al. [73] have
studied the effects of injection-moulding processing parameters on acetaldehyde
generation and degradation of PET. These authors found that the levels of
acetaldehyde in preforms increase with increasing processing temperature, shear rate,
back pressure and overall residence time.
Nerin et al. [74] have analysed extracts obtained by supercritical fluid extraction of
virgin and recycled PET by GC-MS. Degradation products that have been observed
are dimethyl terephthalate and methylethyl terephthalate.
Studies on model compounds showed that benzoic acid and esters are products of
thermal degradation, while benzoic acid and aliphatic acids, anhydride and alcohols are
due to thermo-oxidative degradation [75].
Thermal stability studies of PET showed that the major oligomer fraction, i.e. cyclic
(n = 3 - 6), showed only minor concentration changes with heating. Non-cyclic
oligomers showed a marked increase in abundance on heating. Volatiles detected by
GC-MS were p-xylene, butyl benzoate, benzaldehyde, 2,4-dimethylpropylbenzoate,
methylvinyl terephthalate and diethyl terephthalate [76].
Hydrolytic degradation of PET as studied by MALDI showed that untreated commercial
PET contains only cyclic oligomers, which can be generated during the whole
polycondensation process, whereas the linear oligomers formed at first disappear.
During degradation the number of cyclic oligomers decreases strongly. The amount of
linear oligomeric diols as well as mono-acid terminated species increase [77].
The thermal degradation of PET has also been studied by MALDI [78]. The results
indicate the formation of cyclic oligomers that decompose at higher temperatures
(> 320°C). The formation of anhydride containing olig omers could also be detected by
MALDI and NMR as well as the formation of acetaldehyde.
- 45 -
PET packaging has been tested for volatile content after exposure to high
temperatures [79]. Few volatiles (GC-MS) were found for samples composed only of
PET. Degradation products of butylated hydroxytoluene were identified, i.e.
p-benzoquinone, 2,5-cyclohexadiene-1,4-dione-2,6-bis-(1,1-dimethylethyl), 4-(2,2,3,3-
tetramethyl butyl)phenol, 2,6-bis-(1,1-dimethylethyl)-4-ethylphenol as well as
degradation products of PET, i.e. dimethyl terephthalate and methyl vinyl terephthalate.
Other identified compounds were 2-ethyl-1-hexanol, i.e. reagent for manufacture of
DEHP, and p-xylene, i.e. contaminant from terephthalic acid manufacture. More
volatiles from a thermoset PET were identified by dynamic headspace analysis at
200°C [80].
Various authors have also looked at compounds migrating from PET in food or food
simulants. Migrants that have been identified in food or food simulants are ethylene
glycol, PET oligomers, terephthalic, phthalic and isophthalic acids, glycerol, diethylene
glycol, acetaldehyde, acetic acid, propionaldehyde, terephthalic acid and dimethyl
terephthlate [81-85].
3.4.2 2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
PET is usually processed without addition of antioxidants. The stabilisation is mainly
provided by UV absorbers due to the fact that the main PET degradation during use is
photolysis and photo-oxidation. Among the UV absorbers for PET the benzotriazole-
type absorbers are in general the first choice because they exhibit good colour stability
and have themselves a low initial colour. An example of this class of UV absorbers
used in PET is 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, also
known as 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. No
literature specifically dealing with the ageing of this substance was found. However the
general information on the photochemistry of benzotriazoles can be used. This was
described earlier, Section 3.3.7, for 2-(2’-hydroxy-5’-methylphenyl)benzotriazole
[86-88]. The same mechanism of photolysis and photooxidation is expected as was
mentioned of 2-(2’-hydroxy-5’-methylphenyl)benzotriazole. Again benzotriazole is
expected to be the major product of degradation.
3.4.3 Hexanedioic acid polymer with 1,3-benzenedimethanamine

Despite the good properties of PET, like the relatively low permeability to oxygen and
carbon dioxide, packaging applications require even lower gas permeabilities. Various
solutions have been suggested to obtain this. One of the recent developments is the
melt blending with high molecular weight polyamides. This includes the development
- 46 -
of immiscible, lamellar polyamide phases within the PET. This reduces the oxygen and
carbon dioxide permeability by a factor of two or more [8]. This polyamide exhibits gas
barrier properties an order of magnitude higher than that of PET [90].
Yellowing of PET/MXD6 blends has been shown to be proportional to amino end group
concentrations in the polyamide [91]. Recently, a mechanism was proposed which
states that yellowing is dependent upon acetaldehyde. Acetaldehyde condenses with
polyamide amino end groups to produce intermediate (and uncoloured) imines. These
intermediate imines condense with acetaldehyde to produce conjugated imines, which
are the coloured chromophores [92]. The yellowing effect of the PET/MXD6 blend is
stronger compared to the separate polymers. Furthermore the history of the samples
is important, especially pre-drying of the separate polymers prior to co-extrusion results
in less yellowing compared to drying of the PET/MXD6 blend [92].
Reaction and degradation products from hexanedioic acid polymer with

1,3-benzenedimethanamine, used as an acetaldehyde scavenger in PET bottles, are
expected to be very similar to that of e.g. nylon 6 or 6,6. In polyamide C-N bonds have
been shown to be susceptible to cleavage resulting in amino and carboxyl end groups.
The mechanism is thought be primarily a radical pathway (both photo-oxidative and
thermo-oxidative) which produces alpha,beta-unsaturated ketocarbonyl groups, which
may be conjugated with secondary amino groups, ketoimide structures and pyrorolyl
groups [93].
Possible degradation products will be either the monomers, e.g. hexanedioic acid and
1,3-benzenedimethanamine, oligomers or degradation products similar to e.g. nylon
6,6 (e.g. cyclopentanone). No literature was found on reaction products of PET and
hexanedioic acid polymer with 1,3-benzenedimethanamine with the exception of the
yellowing effect as mentioned earlier which is indirectly a reaction product of PET, i.e.
acetaldehyde, and MXD6.
3.4.4 Copper phthalocyanine blue

Phthalocyanine and its metal complexes are a class of compounds with very interesting
properties and have been used as sensing elements, photochemical redox agents and
photosensitisers. Copper phthalocyanine is also used as a pigment in food packaging.
Phthalocyanine is one of the most thermally stable substances due to its extremely
high aromatic character [94]. A few studies investigated the thermal stability of copper
phthalocyanine sheet polymer. The threshold temperature at which major
- 47 -
decomposition occurs is typically higher than 450°C in air. If copper phthalocyanine
fragments under high thermal conditions (> 800°C in nitrogen), various modes of
fragmentation can occur leading to a large variety of low abundance fragments.
Important fragments that could be identified are nitrogen, hydrogen cyanide, and
benzonitrile [95]. Under normal processing conditions or during normal use of
packaging containing copper phthalocyanine blue no significant degradation of the
copper phthalocyanine additive is expected.
3.5 Polyvinyl chloride

3.5.1 General aspects of polyvinyl chloride chemistry
PVC is one of the most widely used plastics in the world and has a wide range of
applications from pipes, fixtures, frames and cables in the building industry to food
wraps, oil bottles and blister packaging in food contact materials. The processing
conditions and the additives used in the formulation control the physical properties of
the plastic. Stabilisers, plasticisers, impact modifiers and lubricants are also often
added to the formulation.
An inherent property of PVC is the low stability due to degradation via zip elimination of
hydrogen chloride (HCl) at relatively low temperatures [96-98]. Stabilisers are added to
the polymer and can be metallic or non-metallic, although non-metallic compounds are
only usually added to enhance the efficiency of the metallic soaps [99]. Metallic
compounds are often organo-tin based and epoxy compounds are commonly used as
non-metallic stabilisers in PVC. Examples include epoxidised sunflower oil (ESO),
epoxidised soya bean oil (ESBO) and epoxidised linseed oil (ELO).
A migration study was carried out by FT-IR on rigid PVC containing ESO, zinc and
calcium stearate as primary stabilisers, and stearic acid as a lubricant [100]. Sunflower
oil and 15% (v/v) aqueous ethanol were used as food simulants but identification of
migrants was difficult due to overlapping bands in the FT-IR spectra. Dissolving the
PVC directly in tetrahydrofuran and evaporating the solvent obtained cleaner spectra.
From this, migration of the metal stearates and the ESO starting materials was
observed.
A long term behavioural study of PVC products under landfill conditions may also
represent a worst case for food contact materials and could give indications of any
potential reaction or breakdown products that may migrate from the plastic [101]. In
simulations PVC flooring showed loss of plasticisers di-(2-ethylhexyl) phthalate and
- 48 -
butylbenzyl phthalate under methanogenic conditions. Calcium and zinc stabilisers
were also detected but were at too low a concentration to be quantified. There was a
loss of the plasticiser di-isononyl adipate from PVC cables.
Through detection of the gases evolved, Bockhorn et al. [102] were able to identify
other breakdown products. Hydrogen chloride and a small amount of benzene were
detected during the first mass loss and the second degradation step saw the remaining
residue decompose into aromatic hydrocarbons.
3.5.2 Dioctyltin bis(ethylmaleate) and dioctyltin bis(2-ethylhexyl thioglycolate)

119
Organo-tin stabilisers are commonly added to PVC and Sn Mössbauer spectroscopy
has been used to investigate the degradation of the tin species. In a study using
gamma-irradiated PVC, the tin stabilisers dioctyltin bis(iso-octylthioglycolate), dibutyltin
bis(iso-octylthioglycollate) and dibutyltin bis(iso-octylthiomaleate) were all seen to
breakdown to the tin tetrachloride species [103,104]. In other investigations dialkyltin
laurates, dialklytin bis(ethylcysteinates), stannous stearate and stannous cysteinate
stabilisers were incorporated in the PVC and the polymer subjected to progressive
thermal degradation at 185°C [105]. The dialkyltin laureates and dialklytin
bis(ethylcysteinates) were converted into dialkyltin chlorides and the stannous stearate
and stannous cysteinate were rapidly converted to stannic oxide and stannic chloride
respectively.
119
Sn Mössbauer spectroscopy was also used in other studies to identify and quantify
the organo-tin species formed in PVC during processing and thermal degradation
[106]. The starting compounds used were dioctyltin bis(isooctylthioglycolate),
monooctyltin tris(isooctylthioglycolate), dioctyltin bis[(2-
ethylhexyloxycarbonyl)methanethiolate] and octyltin tris[(2-
ethylhexyloxycarbonyl)methanethiolate]. In technical PVC foils containing other
ingredients such as ESBO, polymer processing aids and impact modifiers, the tin
containing species after processing were determined to have undergone ligand
exchange and were identified as a mixture of mono- and di-octyl tin compounds that
had undergone ligand exchange with chloride or carboxylate group ligands. Table 8
contains a complete list of products. Similar results were also determined from PVC
shampoo bottles [107].
Tin in the +4 oxidation state forms a large number of inorganic as well as

organometallic compounds (organotin compounds, OTC). OTC have one or more
- 49 -
carbon-tin covalent bonds that are responsible for the specific properties of such
molecules. There are four series of OTC depending upon the number of carbon-tin
bonds. These series are designated as mono-, di-, tri- and tetra-OTC compounds with
the general structure RnSnX4-n where R is an alkyl or aryl group, and X is a singly
charged anion or an anionic organic group. Mono- and di-OTC are chemically reactive
and are thus used as stabilisers of PVC, as well as catalysts in the production of
polyurethane and in the cold-curing of silicon elastomers [108].
(i) Mercaptides and organo-tin sulfides

The general structure is:
R'
S
R Sn S
S R'
R'
where
–S—R’ = mercaptan
–S—(CH2)n—CO—O—R’ = mercapto ester
–S—(CH2)n—O—CO—R’ = reverse ester
(ii) Organo-tin carboxylates and maleates

The general structure is:
R
R Sn O O
O O
R'
R'
where
–O—R’ = alkoxy
–O—CO—R’ = carboxylic acid
–O—CO—CH=CH—CO—O— = maleate
–O—CO—CH=CH—CO—O—R’ = maleate ester
Commercial organotin compounds are usually pure since, for technological reasons,
care must be taken to avoid metal contamination during manufacture. The impurities
are primarily solvent residues remaining from the product purification and separation
- 50 -
processes. OTC may be readily synthesised using Grignard reaction technology. The
most common PVC stabilisers are produced by reaction of mono- and dialkyltin
chlorides with mercapto esters.
In general, OTC may be degraded both chemically and biochemically. Hydrolytic

decomposition occurs at rather extreme pH values unless there are other catalytic
influences including photochemical. The C-Sn bond is susceptible to nucleophilic and
electrophillic attack e.g. through acid- and base-mediated hydrolysis, solvolysis and
halogenation. Dialkyltin compounds may react spontaneously with air and moisture to
form dialkyl hydrated oxides [109].
The C—Sn bond has little influence on the stabilising performance of the OTC in PVC
but determines the toxicological characteristics of the final molecule. Organotin
mercaptides and carboxylates are characterised by S-Sn and O-Sn bonds respectively.
This part of the molecule is effectively responsible for the mechanism of PVC
stabilisation and determines the behaviour of the stabiliser during PVC processing.
Organotin carboxylates are less efficient as heat stabilisers than the corresponding
mercaptides. Moreover, the latter will react readily with heavy metals such as lead and
cadmium to form inorganic sulfides.
The stabilisers act as HCl scavengers through the formation of the corresponding tin
chloride. They can also eliminate and/or replace labile allylic chlorides formed via the
loss of HCl from PVC, which initiate dehydrochlorination. OTC can also act as
antioxidants.
Colour development in PVC can be interrupted by addition of mercaptide acids on

polyenes by defect site destruction and Diels-Alder reactions.
Thermal oxidative degradation reactions are important because reactive free radicals
may be formed initially from PVC chain scission. The presence of oxygen can also
cause dehydrochlorination involving complex mechanisms and reactive species. In the
absence of oxygen, the most important reaction is a Diels-Alder reaction which leads to
polymer branching
3.5.3 Epoxidised soya bean oil

ESBO is used as a heat stabiliser and plasticiser in PVC films and gaskets. ESBO is a
mixture of substances that is produced by the controlled epoxidation of soya bean oil in
- 51 -
which the C=C double bonds are largely converted to epoxy groups. The major
unsaturated fatty acids in soybean oil triglycerides are 7% linolenic acid, C18:3; 51%
linoleic acid, C-18:2; and 23% oleic acid,C-18:1 this equates to ca. 4.5 unsaturated
bonds per triglyceride molecule. It also contains the saturated fatty acids stearic acid
and 10% palmitic acid. ESBO may contain small amounts of other fatty acid residues
other than C18, both saturated and unsaturated, and hydroxyls. Typical acidity value is
ca 0.4 mg KOH/g due to free fatty acids.
ESBO exerts its stabilising effect by reacting with HCl arising from the
dehydrochlorination of PVC, to form hydrochlorin products:
O OH
+ HCl
Cl
Model studies have shown that epoxidised compounds can react with allylic chlorine
via O-alkylation to form allylic chlorinated ethers [110]. These reaction products react
readily with HCl to restore the allylic chloride.
While the three-membered oxirane ring systems are fairly stable to oxidation, they
undergo rapid degradation at higher temperatures (> 250°C) where the oxirane ring is
broken to give polymeric oxidation products [111].
Notwithstanding steric factors, the oxirane rings of ESBO can be opened with
nucleophiles (including alcohols and water) under acid catalysis to form a series of
polyols or alkoxy-ols.
Biswas et al. [111] have reported on the ring opening aminolysis of ESBO in the
presence of a weak Lewis acid (ZnCl2). The reaction proceeded via ring opening but
did not lead to significant cross-linking. Stronger Lewis acids were reported to react
more effectively with the epoxy group leading to enhanced electrophilicity of the two
carbon atoms of the epoxy moiety resulting in a variety of amine-initiated polymeric
products.
- 52 -
3.5.4 Stearic acid
Stearic acid is used as an emulsifier for PVC. No purity specification has been found.
Other saturated fatty acids may exist as impurities in the stearic acid, especially if
derived from natural sources.
Since stearic acid is saturated it does not undergo autoxidation except at very high
temperatures. Under acidic conditions, any carboxylic acid can react with hydrogen
peroxide or other O-donating oxidant, to form the peroxy acid, which can break down to
the corresponding alcohol and acid with accompanying evolution of oxygen:
RCOOH + H2O2 RCO3H + H2O RCO2H + 1/2O2
Peroxy acids are reactive and can oxidise e.g. alkenes to epoxides, thioethers to
sulfoxides and sulfones, and tertiary amines to amine oxides.
3.5.5 Acetyl tributyl citrate

Acetyl tributyl citrate (ATBC) is a plasticiser used in PVC films and sealing gaskets. A
typical specification for ATBC is acid value 0.2 mg KOH/g, moisture 0.25% and heavy
metals 1 ppm.
Partial hydrolysis of the butyl esters will yield the corresponding free carboxyl moiety on
the citric acid molecule and n-butanol. Hydrolysis of the acyl moiety will yield the free
hydroxyl group on citric acid and acetic acid. When the hydrolysis is carried to
completion, the products are n-butanol, acetic acid and citric acid:
O
H3C COOnBu H2 O / H+ COOH O
O COOnBu HO COOH + H3C + 3 nBuOH
COOnBu COOH OH
3.5.6 Paraffin wax

Paraffin wax is a refined mixture of solid, saturated hydrocarbons, mainly branched
paraffin, obtained from petroleum. PVC lubricants consist of paraffin wax alone or in
combination with calcium stearate and/or oxidised polyethylene wax. Usage levels are
usually in the range 0.5-3%.
- 53 -
Fully refined paraffin wax contains less than 0.5% oil. The use of waxes in plastic
packaging materials is subject to Commission Directive 2002/72/EC relating to plastic
materials and articles intended to come into contact with foodstuffs. The specification
given in Annex V of this Directive states:
“Waxes, refined, derived from petroleum based or synthetic hydrocarbon feedstocks.
The product should have the following specifications:
- Content of mineral hydrocarbons with Carbon number less than 25, not more
than 5 % (w/w)
- Viscosity not less than 11 × 10–6 m2/s (= 11 centistokes) at 100 °C
- Average molecular weight not less than 500.”
3.6 Polyamide
3.6.1 General aspects of polyamide chemistry
Over one hundred different formulations are available for the production of polyamides,
but of those used in food contact materials polyamide 6,6 (also called nylon 6,6) is the
most common. The increasing use in food contact materials is due to the physical
stability of PA 6,6 at temperatures used to cook food and this leads to uses such as
cooking bags, baking sheets and nylon cooking utensils. Data on reaction and
breakdown products during PA 6,6 production and fabrication are scarce in the
literature, so inferences are made from the thermal degradation studies reported. The
PA 6,6 synthesised for this project has a fairly simple formulation with only talc, as a
mineral filler, and zinc stearate, as a mould release agent, as ingredients. This means
that any degradation products seen are likely to originate from the polyamide backbone
itself and not because of interactions between the ingredients.
One paper reported detection of hydrogen cyanide (HCN) from pyrolysis and
thermooxidative degradation of a number of nitrogen-containing polymers including PA
6,6 [112]. The amounts of HCN formed ranged from <0.1% at 600oC to 10% at 1200oC
for pyrolysis and 0.2% at 600oC to 9% at 1200oC for thermooxidation.
Studies were carried out on plastic bags containing PA 6,6, of the type used for food
contact materials [113]. The bags were held at 200oC for 2 hours in a flask containing
a Tenax trap. The thermal decomposition products were washed from the trap using
diethyl ether and identified using headspace GC-MS. Three products were detected
and they were cyclopentanone (6.6 mg/g), 2-cyclopentylcyclopentanone (3.6 mg/g) and
2-ethylcyclopentanone (< 0.1 mg/g). The same results were observed using PA 6,6 in
an unprocessed form. It was proposed that the cyclopentanone was formed from the
- 54 -
decomposition of the adipic acid end-groups through a complex mechanism that is not
fully understood.
Later studies suggested that the quantification carried out on

2-cyclopentylcyclopentanone may have been erroneous due to incomplete desorption
from the PA matrix [103,104]. Using an improved test method showed higher
concentrations of 2-cyclopentylcyclopentanone, 1.44 – 15.6 µg/g, for a range of
different grade PA 6,6 plastics.
The effects of PA plastics undergoing thermal and thermooxidative degradation after

consecutive recycling was investigated using differential scanning calorimetry, FT-IR
and headspace solid phase micro-extraction GC-MS (HS-SPME-GCMS) [105]. The
HS-SPME-GCMS identified twenty degradation products that were separated into four
groups: cyclic imides, pyridines, chain fragments and cyclopentanones. These
compounds are given in Table 9, for the unrecycled plastic. This investigation helped
to show the origin of some of the breakdown products. There are comprehensive
reviews in the literature investigating and explaining the different mechanisms thought
to be taking place to form many of the products described [106,107]. However, there is
still much debate and disagreement about which mechanisms are actually operating.
3.6.2 Zinc stearate

The zinc salt of octadecanoic acid is an additive which acts as an antioxidant and
stabiliser in the plastic. It is also used as a mould release agent. It is postulated that
zinc stearate competes with metal ions to reduce the number of high energy sites
available for bonding at the metal surface. As the metal surface energy is reduced,
mould release is improved. At levels of addition above 1000 ppm, zinc stearate can
interfere with the performance of other polymer processing additives.
The exact composition of the zinc stearate depends upon the source and purity of the
fatty acid used (generally 90-100%) and may contain zinc palmitate, zinc oxide (13-
15%) and up to 2% free fatty acids (predominantly C18 and C16), as well as moisture
(3%) and total ash (10%). The specification for the BP grade lists limits for alkali and
alkali earth metals (< 1 ppm), and heavy metals (As < 1.5 ppm, Pb < 10 ppm, Cd
< 15 ppm).
Zinc stearate is generally stable under ordinary conditions of use and storage. Zinc
stearate is practically insoluble in water, alcohol and ether, and slightly soluble in
- 55 -
aromatic and chlorinated solvents. It is decomposed by dilute acids to give stearic acid
and the corresponding zinc salt. It is reactive to aggressive reagents such as strong
acids, strong alkalis and peroxides.
Zinc stearate can undergo alcoholysis in the presence of a catalyst to give the
corresponding fatty acid ester and zinc hydroxide:
[RĆOO]2Zn + 2X´ÓH 2 RĆOOX´´ + Zn(OH)2
Under acidic conditions (e.g. H2SO4, HCl, BF3), the reaction proceeds via the
carboxylate anion, whereas the alkaline mediated alcoholysis proceeds via the alkoxide
anion (e.g. with NaOCH3).
3.6.3 Talc
Talc is a hydrated magnesium sheet silicate with the chemical formula Mg3SiO10(OH)2.
The sheet is composed of a layer of magnesium-oxygen/hydroxyl octahedral,
sandwiched between two layers of silicon-oxygen tetrahedra. The main or basal
surfaces of this sheet do not contain hydroxyl groups or active ions, which explain its
hydrophobicity and inertness.
Talc is a filler commonly used as a reinforcer in certain polymers. It is used to increase

heat deflection temperature and stiffness, and can reduce creep, shrinkage and the
coefficient of linear thermal expansion. Talc also gives a conventional nucleating
effect. In plastics it gives a good balance of rigidity and impact strength. Advanced
milling technology is used to obtain the finest talcs without reducing the reinforcing
power of the lamellar structure. High purity gives very good long-term thermal stability,
making talc good for use in packaging (including odour-sensitive food-contact
applications). With whiteness and low yellow index, talc-filled compounds are easier to
colour, with a reduced pigment requirement. Some grades will also reduce shrinkage
and warpage in larger mouldings.
Talc ores differ according to their mineralogical composition and are divided into two
main types of deposits: talc-chlorite and talc-carbonate. Talc-chlorite ore bodies
consist mainly of talc (sometimes 100%) and chlorite, which is hydrated magnesium
and aluminium silicates, and is more hydrophilic than talc. Talc-carbonate ore bodies
are mainly composed of talc-carbonate with traces of chlorite. The carbonate is
typically mixtures of magnesium and calcium carbonate, which is removed to produce
- 56 -
pure talc concentrate. The most common impurities present in talcs are CaO (up to
8%) and Al2O3 (up to 6%) with small amounts of sodium, alumina and iron.
Apart from pharmaceutical and cosmetic uses, talc is also a permitted food additive in
the EU (E553b) and as such must meet certain purity criteria for this use. It is
permitted to contain varying proportions of associated minerals such as alpha-quartz,
calcite, chlorite, dolomite, magnesite and phlogopite.
Talc is considered to be essentially inert and non-toxic. It is practically insoluble in

water, weak acids and weak alkalis but does have a marked affinity for certain organic
materials. It has the ability to adsorb certain organic chemicals and therefore is used
as a carrier for organic substrates in some industrial applications.
4. THEORETICAL LIST OF POSSIBLE IMPURITIES / DEGRADATION

PRODUCTS / REACTION PRODUCTS
The theoretical lists of impurities, degradation and reaction products are listed in
Tables 10 to 15 for the six polymers. This list was produced from the results of the
literature search reported in Section 3 as well as in-house knowledge derived from
experience in the analysis of food contact materials and articles.
5. ANALYSIS OF THE TEST POLYMERS

Samples and extracts of the polymers containing no additives were prepared in the
same way as for those polymers containing the additives. All samples and sample
extracts were prepared in duplicate.
Analysis was carried out by thermodesorption GC-MS (all polymers) to detect any very
volatile substances, solvent extraction followed by GC-MS (all polymers) and GCxGC-
TOF-MS (PP, HDPE, PS, PET and PA) to detect any semi-volatile substances and
solvent extraction followed by LC-MS (LC-TOF-MS was used for the HDPE, PVC and
PA polymers and LC-FT-MS was used for the PP, PS and PET polymers) to detect any
polar and/or non-volatile substances present in the plastics. NMR analysis was also
carried out on extracts of all six polymer types. With this combination of techniques a
wide variety of components can be detected, e.g. polar/non-polar, small molecules up
to MW 1,000 Da. A molecular weight of 1000 Da is generally accepted (e.g. by the
- 57 -
EFSA-AFC panel) as the molecular weight above which migrants are not considered to
be of concern due to the absence of potential for absorption in the gut.
5.1 Sample preparation

5.1.1 Sample preparation for thermodesorption GC-MS
HDPE, PVC and PA - 0.25 dm2 of sample (taking into account both sides of these thick
test polymers) was cut into small pieces and transferred to a 10 ml headspace vial.
Internal standard (10 µl of 1.0 mg/ml solution of fluorobenzene) was added and the
vials were capped.
PP, PS and PET - 0.25 dm2 of sample (taking into account both sides of this thick test
polymer) was cut into small pieces and transferred to a 20 ml headspace vial and
internal standard (1 µl of 1.3 mg/ml solution of fluorobenzene) was added.
5.1.2 Sample preparation for GC-MS and GCxGC-TOF-MS

1 dm2 of sample (taking into account both sides of this thick test polymer) was cut into
small pieces and transferred into a glass vial. Extraction solvent (20 ml), both ethanol
and isooctane were used for all polymers, was added and the vials were capped and
incubated for 24 hours at 60°C with occasional shak ing. Internal standards were
added to achieve a concentration in the extract of 2 µg/ml. d5-Phenol, d35-stearic acid,
d4-DEHP and d6-benzene were added to the extraction solvents used for the PP, PS
and PET test polymers. d10-Benzophenone and C17 triglyceride were added to the
extraction solvents used for the HDPE, PVC and PA test polymers. After cooling a
portion (1 ml) of the extraction solvent was transferred to a glass vial for analysis. The
remainder of the extract was concentrated to a final volume of 2 ml under a gentle
stream of nitrogen. The concentrated extract was transferred to a glass vial for
analysis.
Note: the ethanolic extract of the PVC + additives test polymer could not be
concentrated to 2 ml. The final volume was approximately 4 ml. This is proposed
to be due to the presence of a large amount of acetyl tributyl citrate which was
added at a level of 30% to the PVC and which dissolves in ethanol. In isooctane
this was not observed, since the total mass of extractable substances was less with
isooctane than with ethanol for this polymer.
As well as preparing extracts of the test polymers for analysis by GC-MS stock
solutions of the individual additives were prepared at a concentration of 1 mg/ml in both
- 58 -
ethanol and isooctane. For those additives that were not soluble at this concentration a
portion of the saturated solution was taken for analysis.
5.1.3 Sample preparation for LC-MS, LC-FT-MS and LC-TOF-MS

2
1 dm of sample (taking into account both sides of this thick test polymer) was cut into
small pieces and transferred into a glass vial. Extraction solvent, i.e. ethanol or
isooctane (20 ml) was added and the vials were capped and incubated for 24 hours at
60°C with occasional shaking. Internal standards w ere added to achieve a
concentration in the extract of 2 µg/ml. d5-Phenol, d35-stearic acid, d4-DEHP and
d6-benzene were added to the extraction solvents used for the PP, PS and PET test
polymers. d10-Benzophenone and C17 triglyceride were added to the extraction
solvents used for the HDPE, PVC and PA test polymers. After cooling a portion (1 ml)
of the extraction solvent was transferred to a glass vial for analysis. 1 ml of
isopropanol was added to the isooctane extract to make it compatible with the LC
conditions to be used. The remainder of the extract was evaporated to dryness under
a gentle stream of nitrogen. The residue was redissolved in acetonitrile and was
transferred to a glass vial for analysis.
Note: Again due to the high concentration of additives in the ethanolic extract of
the PVC + additives test polymer it could not be evaporated to dryness.
Stock solutions of the additives were prepared at a concentration of 1 mg/ml in

isooctane and ethanol, evaporated to dryness and redissolved in acetonitrile and were
analysed alongside the extracts.
5.1.4 Sample preparation for NMR

PP, HDPE, PET and PA samples with and without additives (0.5 g) were extracted with
2 ml deuterated chloroform containing 0.05% tetramethylsilane (TMS, NMR internal
standard) by shaking overnight at room temperature. Chloroform was selected as the
extraction solvent because of its aggressive extraction properties. This solvent was not
suitable for the extraction of the PS and PVC samples as it dissolved the polymer
thereby not providing samples amenable to NMR spectroscopic analysis. Instead
deuterated methyl sulfoxide (DMSO) containing 0.05% TMS was used (0.5 g polymer
and 2 ml solvent). The extract of the PP + additives samples was cloudy and therefore
this extract and the corresponding control (PP only) were filtered prior to analysis
(0.2 µm, PTFE).
- 59 -
Stock solutions of the additives were prepared at approximately 10 mM (for ease of
comparison, = 2 mg/ml for a substance of MW 200 Da) or as saturated solutions for
those standards with low solubility in the chosen solvent. Standards for PP, HDPE, PA
and PET were prepared in deuterated chloroform and standards for PVC and PS were
prepared in d6-DMSO.
5.2 Analysis
5.2.1 Analysis by thermodesorption GC-MS
The HDPE, PVC and PA samples were incubated for 30 minutes at 100°C. The
resulting volatiles were analysed using an Agilent 6980 gas chromatograph (Agilent,
Palo Alto, CA, USA) coupled with an Agilent 5973inert mass selective detector by
splitless injection of 1 ml of the headspace gas onto an DB-VRX capillary column
(30 m x 0.25 mm i.d. x 1.2 µm film thickness; J & W Scientific, Folson, Ca, USA).
Following injection, the oven was held at 40°C for 1 minute and then raised at
10°C/minute to 320°C. The injector was held at 250 °C. Helium (1 ml/min constant
flow) was employed as the carrier gas. The MS was operated in electron impact mode
with scanned monitoring between 40 - 450 amu.
Thermodesorption of the PP, PS and PET samples was carried out for 30 minutes at
100°C. The resulting volatiles were analysed using an Agilent 6980 gas
chromatograph (Agilent, Palo Alto, CA, USA) coupled with an Agilent 5973 mass
selective detector by splitless injection of 1 ml of the headspace gas onto an AT5-MS
capillary column (30 m x 250 µm i.d., 1 µm film thickness; Alltech, Deerfield, IL, USA).
Following injection, the oven was held at 10°C for 1 minute and then raised at
5.2.2 Analysis by GC-MS

The standard solutions of the additives used in all six polymers and the HDPE, PVC
and PA extracts were analysed by GC-MS using an Agilent 6980 gas chromatograph
(Agilent, Palo Alto, CA, USA) coupled with an Agilent 5973inert mass selective
detector. Splitless injection of 1 µl of extract was carried out into a DB-5MS capillary
column (30 m x 250 µm i.d., 0.25 µm film thickness; J & W Scientific, Folson, Ca,
USA). Following injection the oven was held at 60°C for 5 minutes and then raised at
- 60 -
The ethanol and isooctane extracts of the PP, PS and PET were analysed by GC-MS
using an Agilent 6980 gas chromatograph (Agilent, Palo Alto, CA, USA) coupled with
an Agilent 5973 mass selective detector. Splitless injection of 1 µl of extract was
carried out into an AT5-MS capillary column (30 m x 250 µm i.d., 0.25 µm film
thickness; Alltech, Deerfield, IL, USA) using a programmable temperature vapourising
(PTV) injector (Gerstel CAS4 injector). The temperature of the PTV was 60°C for
ethanol and 80°C for isooctane extracts and was rai sed to 300°C at 2°C/second.
Following injection of the ethanol extracts, the oven was held at 60°C for 5 minutes and
then raised at 10°C/minute to 320°C. For isooctane extracts a start temperature of
80°C was used. Helium (1 ml/min constant flow) was employed as the carrier gas.
The MS was operated in electron impact mode with scanned monitoring between 40 -
450 amu.
Difluorobiphenyl (DFBP) and dicyclohexyl phthalate (DCHP) were added to the PP, PS
and PET extracts at a level of 10 µg/ml. Note that d5-phenol, d6-benzene, d35-stearic
acid and d4-DEHP were added earlier at a level of 2 µg/ml. Of all these internal
standards DFBP, DCHP and d4-DEHP could be positively analysed by GC-MS. d6-
Benzene was too volatile, d5-phenol showed a bad peak shape and d35-stearic acid
was not detected at a level of 2 µg/ml.
5.2.3 Analysis by GCxGC-TOF-MS

GCxGC-TOF-MS analysis was performed using a LECO Pegasus III time-of-flight
mass spectrometer (LECO Corp., St. Joseph, MI, USA). In the first dimension an
AT5-MS capillary column (30 m x 250 µm i.d., 0.25 µm film thickness; Alltech,
Deerfield, IL, USA) was used. This was coupled to a polar BPX50 column
(1 m x 100 µm i.d., 0.1 µm film thickness; J&W Scientific, Folson, CA, USA) in the
second dimension. 1 µl aliquots of the samples were injected in splitless mode using
PTV injection (Gerstel CIS4 injector). The initial PTV temperature was 60°C, and
0.6 minutes after injection, the temperature was raised to 300°C at a rate of 120°C/min
and held at 300°C for 50 min. The initial GC-oven temperature was 60°C (for ethanol
extracts) or 80°C (for isooctane extracts), 3 minut es after injection the temperature was
raised to 325°C with a rate of 6°C/min and held at 325°C for 10 minutes. The
modulation time was 4 seconds.
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5.2.4 Analysis by LC-MS and LC-FT-MS
All isooctane and ethanol extracts of the test polymers and the standard solutions of
the additives were analysed by LC-FT-MS using a Thermo Finnigan LTQ linear ion-trap
system (Thermo Electron, San Jose, CA, USA) consisting of a Surveyor AS
autosampler, Surveyor MS pump and LT-1000 mass detector coupled to Fourier-
Transform mass spectrometer.
The following LC-MS method was used:
- column: Xterra MS C8 column (150 x 3 mm, 3.5 µm)
- mobile phase A: 5 mM NH4Ac (pH 9.5)
- mobile phase B: MeCN + 1 ml 5 mM NH4Ac + 0.5 ml 25% NH4OH
- ethanol extracts: 90% A to 0% A in 20 minutes, 0% A (10 min)
- isooctane extracts: 50% A to 0% A in 10 minutes, 0% A (20 min)
- APCI positive and negative mode (m/z 150-1500)
- tuning: d4-DEHP (APCI positive mode)
d35-stearic acid (APCI negative mode)
- microscans: 3
- max. injection time: 200 ms
- injection volume: 10 µl
- sample temperature: 15°C
- column temperature: 30°C
-flow: 400 µl/min
- APCI source:
- Vaporiser temperature: 400°C
- Sheat gas 30
- Aux gas 5
- Sweep gas 0
- Discharge current 4 µA
- Capillary temperature 250°C
- Capillary voltage (V): 24 (+), -45 (-)
- Tube lens (V): 65 (+), -110 (-)
All system control, data-acquisition and mass spectral data evaluation were performed
using XCalibur software version 1.4. The mass accuracy was better than 1 ppm.
5.2.5 Analysis by LC-TOF-MS

All isooctane and ethanol extracts of the test polymers and the standard solutions of
the additives were concentrated and resuspended in acetonitrile to provide a vehicle
- 62 -
compatible with the selected mobile phases. The extracts were analysed by LC-TOF-
MS using an Agilent LC/MSD TOF (Agilent, Santa Clara, California, USA) consisting of
a 1200 Series LC and a time of flight mass spectrometer. Two separate LC-MS
methods were used in order to increase the coverage compounds that could be
detected in this way. In both cases separation was facilitated using an Agilent
ZORBAX Eclipse XDB-C18 100 x 2.1 mm, 3.5 µm column. For positive mode
electrospray the mobile phase consisted of 0.1% aqueous acetic acid (channel A) and
acetonitrile (channel B). For negative mode electrospray the mobile phase was 5 mM
ammonium formate at pH 5.5 (channel A) and 0.1% 5 mM ammonium formate at
pH 5.5 in acetonitrile (channel B). The mobile phase gradient for both positive and
negative mode electrospray was the same: a starting mixture of 80% A and 20% B that
changed to 50% B over 25 min. This was held for 20 minutes and then went to 100%
B at 60 minutes. This was held for a further 10 minutes before returning to 20% B over
10 minutes. The flow rate was 0.2 ml/min with an injection volume of 5 µl.
TOF-MS analysis was carried out in positive and negative mode electrospray with
nebuliser pressure 45 psi, capillary 4000 V, gas temperature 325oC, drying gas flow at
10 L/min, skimmer 60 V, fragmentor 150 V and octopole RF voltage 250 V. The mass
range measured was 100 – 1100 m/z. The TOF-MS data produced was processed
using Agilent Molecular Feature Editor (MFE) software and parameters are given in
Table 16.
5.2.6 Analysis by NMR

5.2.6.1 CDCl3 extracts
Spectra were acquired at a central frequency of 500.1323546 MHz using a 90°
observation pulse length of 7.5 µseconds and a delay between transients of
12 seconds. 60,000 complex data points were acquired at a controlled temperature of
300K over a spectral width of 20 ppm, giving an acquisition time of 3 secs. Eight
unrecorded (dummy) transients and 1024 transients were used giving a total
experiment time of approximately 2 hours.
5.2.6.2 DMSO extracts

Spectra were acquired at a central frequency of 500.1323546 MHz using a 90°
observation pulse length of 7.5 µseconds and a delay between transients of
17 seconds. 60,000 complex data points were acquired at a controlled temperature of
300K over a spectral width of 20 ppm, giving an acquisition time of 3 secs. Eight
- 63 -
unrecorded (dummy) transients and 512 transients were used giving a total experiment
time of approximately 3 hours.
5.2.6.3 2D NMR spectroscopy acquisition parameters

13
C – 1H Heteronuclear Single Quantum Correlation (HSQC) spectra:
1
H sweepwidth: 13.3298 ppm
13
C sweepwidth: 179.9964 ppm
JCH : 145 Hz
Number of scans: 8
Number of increments: 1
D1: 2 secs
Number of points collected in F2: 1536
Acquisition time: 0.115 secs
Experiment time: 2 hours 26 minutes
1
H – 1H Total Correlation Spectroscopy (TOCSY) spectra:
F2 1H dimension: 15.0110 ppm
1
F1 H dimension: 15.0000 ppm
TOCSY spin-lock time: 0.1 secs
Number of scans: 8
Number of increments: 1
D1: 2.5 secs
Number of points collected in F2: 8192
Acquisition time: 0.5458 secs
Experiment time: 3 hours 35 minutes
6. COMPARING THE IDENTITIES OF THE EXTRACTABLES DETECTED WITH

THE PREDICTED SUBSTANCES
To determine those substances arising from the additives themselves, their impurities,
their reaction products or their breakdown products the chromatograms were
compared. Any peaks detected in the total ion current (TIC) chromatograms derived
from the analysis of the polymer + additive samples that were not present in the
extracts of the polymer only samples were recorded.
- 64 -
6.1 Volatile substances detected by thermodesorption GC-MS
All duplicate experiments showed very similar chromatograms. Figures 1 to 6 show the
TIC chromatograms resulting from the analysis of the PP, HDPE, PS, PET, PVC and
PA samples respectively and the same polymers with additives.
The peaks in the chromatograms of the PP only samples could all be assigned to
alkanes, i.e. oligomers. No additional peaks could be observed for PP + additives
compared to PP.
Two peaks were detected in the TIC chromatograms of the HDPE + additive samples
that were not detected in the corresponding chromatograms of the HDPE only
samples. The mass spectra of each of these additional peaks were derived and
compared with the National Institute of Standards and Technology (NIST) library. The
best matches offered by this comparison were further considered by eye to allow the
best match to be identified. The best library matches of these peaks were: 1-hydroxy-
2-propanone (retention time 11.5 minutes, Figure 7) and propylene glycol (retention
time 12.9 minutes, Figure 8). Neither of these substances were included in the
predicted list of reaction and breakdown products for this polymer (Table 11). The
estimated concentrations were 4 and 144 µg/dm2 for the peaks at 11.5 and
12.9 minutes respectively. All other peaks were detected in both chromatograms.
Several were present in the internal standard procedural blank samples (i.e. no
polymer) the remainder were short chain alkanes derived from the HDPE.
The peaks visible in the chromatograms of the PS samples were identified as styrene
and other substituted benzene-compounds. Due to the number of isomers of the
substituted benzene compounds the specific identities could not be determined.
However, these compounds were observed for both the PS and the PS + additives
samples and thus no additional peaks were observed for PS + additives.
The chromatograms of the PET samples only showed some minor peaks which were
also observed in blank measurements (internal standard only, i.e. no PET polymer).
Hence, no volatiles were observed that could be assigned to PET or additives.
Three peaks were detected in the total ion chromatograms of the PVC + additive
samples that were not detected in the total ion chromatograms of the PVC only
samples. The mass spectra of each of these additional peaks were derived and
compared with the NIST library. The best library matches of these peaks were: ethanol
- 65 -
(retention time 7.0 minutes, Figure 9), 1-butanol (retention time 11.2 minutes, Figure
10) and 2-ethyl-1-hexanol (retention time 19.1 minutes, Figure 11). The other two
peaks detected in the PVC + additive chromatograms were also detected in the PVC
only chromatograms. The best library matches for these substances were methyl
acetate and acetic acid. Additional peaks were detected in the PVC only samples but
were not in the PVC + additive samples. This suggests that these volatile substances
were lost and/or reacted with other substances present when the PVC was mixed with
the additives. All three substances detected in the headspace above the PVC +
additive samples that were not in the control were included in the predicted list (2-ethyl-
1-hexanol derived from di-n-octyltin-bis(ethylhexylthioglycolate), ethanol derived from
di-n-octyltin-bis(ethylmaleate) and 1-butanol from ATBC). The estimated
concentrations were 1850, 1744 and 306 µg/dm2 for the peaks at 7.0, 11.2 and
19.1 minutes respectively.
Cyclopentanone and 2-cyclopentylcyclopenatanone were detected in the headspace

gas above the PA samples with and without additives. The other peaks visible in the
chromatograms (Figure 3) were also detected in the internal standard procedural blank
samples. No peaks were detected in the PA + additive samples that were not present
in the PA only samples.
Identities were proposed for all additional peaks detected in the HDPE and PVC by
thermodesorption GC-MS. The PP, PS and PA did not show any additional volatile
compounds in the samples with additives that could be assigned to either the additives
themselves or degradation/breakdown products. The PET and PET + additive samples
did not release any volatiles. As there were no unidentified peaks then it was not
considered necessary to analyse the additives themselves using this technique.
6.2 Semi-volatile substances detected by GC-MS and GCxGC-TOF-MS

6.2.1 Additives
Standard solutions of the various additives prepared in ethanol and isooctane at
concentrations of 1 mg/ml were analysed by GC-MS. Annex 1 shows the mass spectra
of all peaks detected in the chromatograms (not in the procedural blanks) with a
signal:noise ratio of greater than 3:1. No peaks were detected in the extracts of the
two PA additives (zinc stearate and talc). The analysis of the additives in this way
identifies the impurities present as well as any breakdown products that form during the
solvent extraction step. Many of the additives showed additional peaks in the
chromatograms that were not attributed to the additives themselves but were impurities
- 66 -
or breakdown products. For example the ethanol extracts of the erucamide used as a
slip agent in the HDPE test sample was also found to contain other fatty acid amides
and esters as impurities, therefore this increases the number of possible reaction and
breakdown products from those given in Table 11 where only the reaction and
breakdown products of the erucamide itself were proposed. No good library matches
could be obtained for some of the substances detected and their identities remain
unknown.
Not all of the additive compounds were detected when the extracts were analysed
(Table 17). This may be due to the high molecular weight of the additive, i.e. they were
not volatile enough to be amenable to analysis by GC-MS, or their insolubility in the
extraction solvent, i.e. some additives are inorganic. Because methods were not
available to determine all additives then the proposed mass balance approach to
determine the missing fraction was not followed.
6.2.2 Samples
All duplicate dilute ethanol and isooctane extracts of the polymer and polymer +
additive samples were analysed directly by GC-MS. Based on the GC-MS analysis of
these dilute extracts, it was decided which of the concentrated extracts could be
analysed without damaging or disturbing the GC-MS system.
In most cases the chromatograms obtained from the analysis of the duplicate sample
extracts were very similar. This was not the case for the duplicate PVC extracts and
the duplicate PVC + additive extracts where although the same peaks were detected in
the two sets of chromatograms the estimated concentrations were quite different.
The chromatograms obtained from the analysis of the polymer + additive samples were
compared with the chromatograms obtained from the analysis of the polymer only
control samples and any additional peaks present in the TIC of the polymer + additive
samples were recorded. In all cases the chromatograms obtained from the analysis of
the polymer only control samples did contain some peaks. Where these peaks were
the same additives, impurities or reaction/breakdown products as those formed during
the preparation of the polymer + additive samples it was not possible to identify them
as additional peaks using the approach described. The ions present in the mass
spectrum of each additional peak detected in the TIC of the polymer + additive extracts
were specifically searched for in the chromatograms of the additives to confirm whether
- 67 -
the substances detected were present in the additives themselves or if they were
formed during processing, i.e. reaction/breakdown products.
6.2.2.1 Polypropylene
The chromatograms obtained from the GC-MS analysis of ethanol and isooctane
extracts of the PP and PP + additive samples are shown in Figures 12 and 13
respectively. Only the concentrated ethanol extracts were analysed for the PP and PP
+ additive samples (Figure 14) as it was expected that the concentrated isooctane
extracts would contaminate the system. The dilute isooctane extracts were considered
to be of sufficient concentration to determine the presence of any additional peaks.
In the chromatograms of the isooctane extracts of the PP the patterns of peaks of PP

oligomers were clearly visible (Figure 13). These oligomers were also detected in the
concentrated ethanol extracts (Figure 14). In the extracts of PP + additive samples
several additional peaks were visible in the GC-MS chromatograms that could not be
seen in the chromatograms of the PP only extracts. This was the case for both the
ethanol and isooctane extraction solvents. However for the different extracts different
additional peaks were observed. This was expected, the two solvents were selected
due to their different polarities and therefore their abilities to extract both polar (ethanol)
and non-polar (isooctane) additives, impurities, reaction and breakdown products. The
additional peaks were further identified and their concentrations estimated. Table 18
shows a list of the additional peaks observed in extracts of the PP + additives samples
including their (tentative) identities and estimated concentrations. The EI spectra of all
55 of these substances are given in Annex 2 (PP1 – PP55). Degradation products of
pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), tris(2,4-di-tert-
butylphenyl) phosphite, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-
butanedioic acid) and poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-
[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-
piperidinyl)imino]] were observed. Furthermore it is indicated in Table 18 whether the
compounds observed were predicted. Three compounds were the additives
themselves, a further ten were predicted reaction or breakdown products, the
remaining 42 were not predicted. Seventeen of the unpredicted substances in the PP
+ additive sample extracts had their identities proposed.
The estimated concentrations of those substances detected in the PP + additive

extracts that could not be assigned to the additives themselves, i.e. they were present
either as impurities in the additives, as breakdown products of the additives formed as
- 68 -
a result of the extraction processes or as reaction/breakdown products formed during
the polymer processing, were in the range 2.5 to 17885 µg/dm2. These concentrations
are equivalent to worst case migration values in the range 15 to 107310 µg/kg
assuming, as is the convention, that 1 kg of food is packaged in 6 dm2 of plastic. This
worst case migration assumes total transfer from the plastic. A more realistic migration
level was calculated by applying a generally recognised migration model. The results
of which are described in Section 7.
6.2.2.2 High density polyethylene

The chromatograms obtained from the GC-MS analysis of ethanol and isooctane
extracts of the HDPE and HDPE + additive samples are shown in Figures 15 and 16
respectively. Both the concentrated ethanol and isooctane extracts were analysed
(Figures 17 and 18).
Many of the peaks observed in the chromatograms of the extracts of the HDPE
samples can be assigned to HDPE oligomers. The substances that were only detected
in the extracts of the HDPE + additive samples are listed in Table 19. In total 80 peaks,
with peak heights greater than 3 x signal:noise ratio, were observed in the
chromatograms of the extracts of the HDPE + additive samples that were not present in
the HDPE control samples. Some of these peaks resulted from the co-elution of two
substances such that in total 87 substances were detected. Of the 22 peaks (25
substances) detected in the ethanol extracts of the HDPE + additive samples three
could be attributed to the additives themselves and 12 to their impurities. More
substances were detected in the isooctane extracts as this non-polar solvent interacts
more strongly with the polyethylene. 74 peaks (consisting of 81 substances) were
detected in the isooctane extracts of the HDPE + additive samples that were not
present in the HDPE control samples. Of these 31 could be attributed to the additives
and their impurities. The remainder are reported in Table 19 as reaction / breakdown
products. However it also remains a possibility that they are present in the additives
themselves but not at a high enough concentration to be detected in the 1 mg/ml
solutions. Where good library matches were obtained for the reaction and breakdown
products or where the structure was found to be related to one of the known additives
this information is also recorded in Table 19. The EI spectra of all 80 peaks detected in
the HDPE + additive extracts that were not present in the HDPE extracts are given in
Annex 2 (HDPE1 – HDPE80).
- 69 -
Table 19 also provides the estimated concentrations of the additives, their impurities
and the reaction and breakdown products detected. Although the identities of some of
the substances are not known the significance of the levels extracted in terms of their
migration into food is discussed in Section 7. The estimated concentrations of the
reaction/breakdown products in the extracts were in the range 1.0 to 721 µg/dm2,
equivalent to worst case migration values in the range 6 to 4326 µg/kg.
6.2.2.3 Polystyrene
For PS the GC-MS chromatograms of the ethanol and isooctane extracts are very
similar (Figures 19 - 22). The chromatograms are dominated by a cluster of peaks
around 24 minutes. Furthermore, the insert chromatograms show a broad feature in
the chromatograms around 25 - 30 minutes. This might be due to the fact that the
material is high-impact PS, i.e. a graft copolymer of polystyrene and polybutadiene,
and the broad feature is due to polybutadiene oligomers. Some additional peaks can
be easily seen in the PS + additives extracts that could be assigned to the PS
additives. Table 20 gives an overview of all additional peaks observed for PS +
additives. Three of the 20 substances detected were the additives themselves and a
further three were predicted. Identities were proposed for 11 of the substances
detected. Although no good library matches were obtained for PS5 – PS13 the origin
of these substances was known in that they were present in the TNPP standard. The
EI mass spectra of all peaks detected in the PS + additives extracts that were not
detected in the PS extracts are shown in Annex 2 (PS1 – PS21).
Of the 20 peaks that were only detected in the PS + additive sample extracts only three
were reaction / breakdown products that formed solely as a result of the polymer
formation. The remainder were all detected in the additives, either as the additives
themselves or as impurities. The estimated concentrations of these reaction /
breakdown products were in the range 0.75 – 5 µg/dm2. Assuming total transfer this
equates to a worst case migration of between 4.5 and 30 µg/kg. The predicted
migration from this polymer is modelled in Section 7.
6.2.2.4 Polyethylene terephthalate

For PET and PET + additives extracts only a few peaks were visible in the
chromatograms (Figures 23 and 24). For those figures in which the baseline noise is
visible a ‘zoomed in’ version is not presented. Analysis of the concentrated extracts
showed some more peaks although the number of additional peaks found for PET +
additives remained low (Figures 25 and 26). Only two additional peaks were observed
- 70 -
for the PET + additives sample extracts as shown in Table 21. The EI mass spectra of
these two peaks are shown in Annex 2 (PET1 – PET2).
One of the two peaks was identified as the 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-

1-phenylethyl)phenol additive. The identity of the second peak was not known, i.e. no
good library match was obtained. The ions observed in the mass spectrum of this
unknown were specifically searched for in the chromatograms obtained from the
analysis of the additives used in the preparation of the PET. Although the same mass
spectrum was not observed similar ions were detected in an impurity present in the
copper phthalocyanin blue and therefore this unknown is proposed to be a reaction
product of this impurity.
The concentration of this substance in the polymer was estimated to be 42.5 µg/dm2.
This is equivalent to a worst case migration of 255 µg/kg assuming, as is the
convention, that 1 kg of food is packaged in 6 dm2 of plastic. This worst case migration
assumes total transfer from the plastic. This is rarely the case for low diffusivity
polymers such as PET. A more realistic migration level was calculated by applying a
generally recognised migration model. The results of which are described in Section 7.
6.2.2.5 Polyvinyl chloride

The chromatograms obtained from the analysis of ethanol and isooctane extracts of the
PVC and PVC + additive samples are shown in Figures 27 and 28 respectively. Due to
the high concentration of additives detected in the ethanol extracts and the resulting
problems with contamination of the GC-MS instrumentation then the concentrated
isooctane extracts were analysed but not the concentrated ethanol extracts.
Few peaks are detected in the extracts of the control PVC samples, however the PVC
+ additive extracts contain in excess of 144 peaks that can be assigned either to the
additives themselves, their impurities or their reaction and/or breakdown products.
The substances detected in the extracts of the PVC + additive samples that were not
detected in the extracts of the PVC only samples are listed in Table 22. In addition to
these many peaks were detected that could be assigned as alkanes originating from
the paraffin wax, these are not included in Table 22. Of the 144 peaks listed (145
substances) one was a known additive and two others were predicted reaction or
breakdown products. Of the remaining 143 substances, consisting of 24 impurities and
115 proposed reaction / breakdown products, identities were proposed for 63. Table
- 71 -
22 also provides the estimated concentrations of the additives, their impurities and the
reaction and breakdown products detected. The EI mass spectra of all peaks detected
in the PVC + additives extracts that were not detected in the PVC extracts are shown in
Annex 2 (PVC1 – PVC144). The estimated concentrations of many of the
impurities/reaction/breakdown products detected in the extracts are high up to
204 mg/dm2. This equates to a worst case migration of 1225 mg/kg.
6.2.2.6 Polyamide
The chromatograms obtained from the analysis of ethanol and isooctane extracts of the
PA and PA + additive samples are shown in Figures 29 and 30 respectively. Both the
concentrated ethanol and isooctane extracts were analysed (Figures 31 and 32). No
additional peaks were detected in the PA + additives samples for any of the extracts.
6.2.2.7 GCxGC-TOF-MS
Analysis of the PVC + additive extracts contaminated the GC-MS system resulting in a
loss of sensitivity and peak resolution. As a result PVC extracts were not subsequently
analysed by GCxGC-TOF-MS. The added value of GCxGC-TOF-MS is the increased
separation due to the second dimension. As a result compounds are not only
separated on volatility but also on polarity. For example, an apolar and polar
compound with the same volatility would elute around the same time in the first
dimension, i.e. GC-MS, however, a second dimension separation on polarity would
resolve them.
For PET and PA 6,6 only the concentrated extracts were analysed as a result of the
outcome of the previous GC-MS experiments, i.e. very few peaks or no additional
peaks were visible for these extracts. Furthermore the PVC extracts were not analysed
as a result of the expected contamination of the equipment as described for the GC-MS
experiments. The concentrated isooctane extract of the PP samples were not
analysed as these were also very concentrated. The GCxGC-TOF-MS chromatograms
of the extracts analysed are shown in Figures 33 to 47.
The GCxGC-TOF-MS data was analysed as follows: first the GC-MS data were
processed as described earlier, next it was verified that if the additional compounds
found with GC-MS were also visible with GCxGC-TOF-MS and finally the GCxGC-
TOF-MS chromatograms were screened visually to identify any previously unseen
compounds.
- 72 -
For the PS, PET and PA it could be easily concluded that no additional compounds
could be detected by GCxGC-TOF-MS (Figures 40 – 47). Due to the limited number of
peaks observed in the extracts for these samples the addition of a second dimension
separation had no added value. Again for the HDPE extracts (Figures 36 - 39) no
additional information was derived. The only exception was the concentrated ethanol
extract of the PP (Figures 33 – 35). In this extract a relatively large amount of PP
oligomers were detected that may make other peaks invisible when measured using
GC-MS. For these samples an increased separation of co-eluting compounds with
GCxGC-TOF-MS has certainly added value. These additional ‘peaks’ are highlighted
in Figure 48. In the GCxGC-TOF-MS chromatograms of PP + additives, 23 additional
peaks could be detected that were not visible with GC-MS (Table 23). All the peaks
detected initially by GC-MS could also be found with GCxGC-TOF-MS although the
(relative) intensity was sometimes different. Table 23 shows the retention times in the
first and second dimensions, the proposed identities of the compounds and whether
they were predicted based on the literature search conducted at the start of this work.
The comparison of GC-MS and GCxGC-TOF-MS was complicated by the fact that the
retention times were different due to the different systems used. Hence, comparison
could only be carried out based on the mass spectra. However, the EI spectra
obtained using a quadrupole GC-MS can differ from the EI spectra obtained with a
TOF-MS, especially with respect to the relative ratios of the different mass traces. The
TOF-MS EI mass spectra of the 23 compounds are shown in Annex 2 (X1 – X23). Of
the 23 peaks, 13 were identified and ten were unknown. Four of these had been
predicted from the literature search. Twelve of these compounds could be identified or
at least assigned to a specific additive. In general the compounds found with GCxGC-
TOF-MS were not visible in GC-MS, even when selected masses were used. This
implicates that the better sensitivity of GCxGC-TOF-MS is the cause of this and not the
increased separation although these two aspects often go hand in hand.
6.3 Non-volatile and polar compounds analysed by LC-MS and LC-FT-MS

6.3.1 Additives
Standard solutions of each of the additives used in the PP, PS and PET were prepared
at concentration of 10 µg/ml in ethanol and isooctane and were analysed using the
method described in 5.2.4. An overview is provided in Table 24. If the additives could
be detected, the corresponding retention time and m/z value are given. Some of the
additives could not be measured using this method including the inorganic additives
like calcium carbonate and additives with a high molecular weight such as poly[[6-
[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-
- 73 -
piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]], and poly(4-
hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid). Commonly
used ionisation techniques in LC-MS like ESI or APCI are considered soft-ionisation
techniques and no fragmentation is expected with these techniques. The combination
of using positive and negative ionisation broadens the range of compounds that can be
detected. There are compounds that can only be ionised in the positive mode, e.g.
amines, while other compounds preferably ionise in the negative mode, e.g. acids.
Furthermore some compounds do ionise in both modes but with different ionisation
efficiency and thus can be detected with different sensitivity in the positive and negative
ionisation mode. Moreover, having two exacts masses, i.e. in positive and negative
mode, of a compound can help in identifying the compound. For example, adduct
formation in one of the two ionisation modes can be easily seen. No impurities were
detected in the extracts as the standard solutions were prepared at low concentration
to avoid system contamination.
6.3.2 Samples
Base peak LC-MS chromatograms of the PP, PS and PET samples are shown in
Figures 49 to 54. As the duplicate samples show very similar chromatograms only one
chromatogram is shown for each sample. Note that the y-axis of the chromatograms is
set at equal values in order to compare the traces obtained from the analysis of the
extracts with and without additives.
Large differences can be seen between the chromatograms of PP and PP + additives

(Figures 49 and 50). For PS and PET only a few peaks are visible in the
chromatograms and only very few additional peaks for the polymers with additives
(Figures 51 to 54). The additional peaks detected in the extracts of the various
polymer + additive samples are summarised in Tables 25 to 27.
For PP a large number of additional peaks were observed although most of them
remained unknown (Table 25). The only exceptions were the additives used in the
samples that could be identified based on their m/z and retention time and the
oxidation product of tris(2,4-di-tert-butylphenyl)phosphite. The concentrated PP
extracts were not analysed by LC-MS due to the high amounts of additives present in
the samples that disturbed the measurements and all measurements thereafter, i.e.
carry-over.
- 74 -
Analysis of the PS samples resulted in six additional peaks for PS + additives. Four of
the six peaks could be assigned to additives used in the samples (Table 26). The peak
with m/z 705.5 was tentatively assigned as oxidised TNPP based on m/z and retention
time. As for the PP the concentrated PS extracts could not be analysed by LC-MS due
to the high amounts of additives present in the samples that lead to severe carry-over
and other disturbances.
For PET only three additional peaks could be observed, one of them being 2-(2H-
benzotriazole-2-yl)-4,6-bis(1-methyl-1-penyl-ethyl)phenol (Table 27). Analysis of the
concentrated PET extracts did not show any peaks in addition to those reported in
Table 27.
For the peaks that could be identified (i.e. the additive standards) the concentrations
were estimated using a calibration solution of the additive in ethanol or isooctane. Note
that these concentrations are only estimates as a single point calibration was used and
in many cases a large extrapolation had to be carried out. These estimated
concentrations are also shown in Tables 25 – 27.
The unknowns reported in Tables 25 – 27 were further investigated by LC-FT-MS in

order to obtain the identity of the peaks. Extracts of the PP, PET and PS samples were
analysed by LC-FT-MS using the method described in Section 5.2.4 with analysis using
an FT-MS system, i.e. a Fourier Transform mass spectrometer, placed behind the LTQ.
The FT-MS system is capable of obtaining high mass resolution, usually < 2-3 ppm.
This high mass resolution was used to identify the unknown peaks found by LC-MS.
From the exact m/z values the possible elemental composition can be determined
which aids in the identification of the otherwise unknown peaks. Tables 28 to 30 show
the additional peaks found for respectively PP, PS and PET samples as described
earlier in the LC-MS section.
Of the 25 unknowns detected in the PP + additive extracts by LC-MS the identities of

eight are proposed following LC-FT-MS analysis. Details of the proposed elemental
composition and the associated mass accuracy are given in Table 28. As in the GC-
MS analysis hexadecanoic acid and octadecanoic acid, proposed to derive from the
glycerol monostearate, and methyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and
ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, impurities in the pentaerythritol
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) additive, were detected. From the
elemental compositions the identities of four other substances are proposed (Table 28).
- 75 -
For PS (Table 29) all of the peaks were tentatively identified. Most peaks could be
assigned to one of the additives used in the samples. One of the unknowns was
tentatively identified as oxidised TNPP (see above). Analysis with FT-MS confirmed
this by showing a corresponding elemental composition. The only remaining unknown,
i.e. m/z 565.5 in the positive ionisation mode, gave an elemental composition of
C36H72O2N2. This elemental composition is identical to that of
N,N-bis(stearoyl)ethylenediamide, an additive used in this PS samples, minus C2H4.
Although it is not clear which compound it is exactly, it can be concluded that it
originates from N,N-bis(stearoyl)ethylenediamide.
For PET (Table 30) many possible elemental compositions could be obtained for the
two unknown peaks and therefore the identity could not be confirmed. The elemental
composition of 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
corresponded correctly with the elemental composition found for the corresponding
peak with an error of only < 1 ppm.
6.4 Non-volatile and polar compounds analysed by LC-TOF-MS

6.4.1 Additives
Standard solutions of the HDPE, PVC and PA additives prepared in ethanol and
isooctane at concentrations of 1 mg/ml (evaporated to dryness and redissolved in
acetonitrile) were analysed by LC-TOF-MS. This instrument provides accurate mass
data for each peak detected in the chromatograms and uses this data to propose
molecular formulae. The LC-TOF-MS system is capable of obtaining high mass
resolution, usually < 5 ppm. The analysis of the additives in this way identifies the
impurities present as well as any breakdown products that form during the solvent
extraction step. Many of the additives showed additional peaks in the chromatograms
that were not attributed to the additives themselves but were impurities or breakdown
products (Tables 31 and 32).
6.4.2 Samples
LC-TOF-MS instrumentation was used to analyse the HDPE, PVC and PA extracts.
Both isooctane and ethanol extracts were prepared. The extracts were then
evaporated to dryness under a gentle stream of nitrogen and redissolved in acetonitrile
(a solvent compatible with the LC-MS mobile phase). The acetonitrile extracts were
then analysed by LC-TOF-MS (as described in Section 5.2.5). The total ion
chromatograms obtained for the extracts are shown in Figures 55 to 58 for HDPE,
Figures 59 – 62 for PVC and Figures 63 to 66 for PA. The regular disturbance seen in
- 76 -
some of the chromatograms is an artefact of the TOF-MS reference mass correction
system.
Some of the chromatographic peaks seen in the samples are very small, but are
elucidated nevertheless, highlighting the power of TOF-MS. Many of the peaks are not
visible from the total ion chromatogram (TIC) but are extracted from the raw data by the
data processing software. No spectral libraries exist for LC-MS data and therefore
identification of unknown substances using this technique is not as straightforward as it
is for GC-MS analysis. The TOF-MS data generated was processed using Agilent
Molecular Feature Editor (MFE) software. This package examines the data, extracts
chromatographic peaks and produces mass spectra for those peaks. The accurate
mass data is then compared to a molecular formula database to predict probable
formulae. Where appropriate the fragment ions have been identified using accurate
mass measurements. This data compliments the structural confirmation from the
accurate mass of the molecular ions. Where more than one molecular adduct was
present the assignment of molecular formulae was simplified as the mass difference
between adducts aided the assignment. For example a mass difference of 5 Da
indicated the presence of M+NH4 (M+18) and M+Na (M+23) and therefore the
numerical value of M (i.e. the molecular mass) was easy to see. Although there is no
ammonia or sodium added to the system these adducts are common to electrospray
ionisation and are thought to arise from impurities in the solvents used as mobile
phases.
The identities of those substances detected in the extracts of the polymer + additive
samples that were not in the control samples are proposed in Tables 33 to 35 for
HDPE and Tables 36 – 39 for PVC along with their estimated concentrations. No
additional peaks were detected by negative ESI for the HDPE + additive isooctane
extracts that were not in the equivalent extracts of the HDPE control samples and there
were no substances detected in the PA + additive samples that were not present in the
PA control samples for any of the modes of analysis. Concentrations of additives
detected in the plastics extracts were estimated relative to the response of the 1 mg/ml
standard solutions. For the reaction and breakdown products the concentrations were
estimated relative to the d10-benzophenone added to the extraction solvent.
6.5 NMR analysis

The NMR data obtained from the analysis of all of the polymer + additive extracts was
directly compared with that for the standards. The resonances in the NMR spectra of
- 77 -
the polymer + additive extracts that were associated with the presence of the additives
and any impurities where thereby identified. Elimination of these resonances, as well
of those for the solvent and the control polymer samples (i.e. polymer with no
additives), enabled resonances resulting from the reaction and breakdown products of
the additives to be identified.
6.5.1 Polypropylene
Of the PP additives, glycerol monostearate, erucamide, diparamethyldibenzylidene
sorbitol, tris(2,4-di-tert-butylphenyl)phosphite, pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate) and poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-
alt-1,4-butanedioic acid), could be detected by 1H-NMR spectroscopy. Due to its
aprotic nature calcium carbonate could not be detected. As no spectral resonances
corresponding to poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-
piperidinyl)imino]] were detected in the extract of the standard it indicates that it was
present at a concentration below the limit of detection (it is unlikely that this high
molecular weight substance dissolved in the CDCl3).
Figure 67 shows the spectra for both extracts (PP control and PP + additives) and the
solvent blank. The PP control and PP + additive spectra can clearly be distinguished in
the form of multiple low intensity resonances in the PP + additive samples that were not
present in the PP control samples. The resonances originating from solvent, PP
control sample and the additives that could be analysed by NMR are compared in
Figure 68. Other resonances, highlighted in Figure 69, were not accounted for which
indicates that they originate from the reaction products or from the breakdown of one or
more of the additives present in PP.

Figure 70 compares the spectra of the HDPE + additives extract with the extracts of the
HDPE control and the solvent blank. Again differences could be observed between the
polymer + additives and the polymer control. Figure 71 shows the resonances that
correspond to the additives that could be detected by NMR, namely oleamide,
octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate, glycerol monooleate and 2,5-bis(5'-
tert.butylbenzoxazol-2-yl)thiophene. Additional resonances, derived from reaction and
/ or breakdown products were observed and these are highlighted in Figure 72.
- 78 -
6.5.3 Polystyrene
Figure 73 compares the spectra for the extracts of the PS with and without additives,
as for the other polymers there are clear differences between the two. Five of the six
additives could be analysed by NMR (DEHP, ethylenebis(oxyethylene)bis-(3-(5-tert-
butyl-4-hydroxy-m-tolyl)-propionate), 2-(2’-hydroxy-5’-methylphenyl)benzotriazole,
polyethylene glycol 4-tert-octyl-phenyl ether, n~5 and polyethylene glycol 4-tert-octyl-
phenyl ether, n=9-10). The sixth additive included in the PS,
N,N-ethylenebisstearamide, was only sparingly soluble in DMSO and as such it is
unlikely to have been extracted from the PS + additive sample. The spectra derived for
the additives are compared with the PS control sample and PS + additives sample in
Figure 74.
The 1H 1D NMR spectra of polyethylene glycol 4-tert-octyl-phenyl ether, n ~ 5 and

polyethylene glycol 4-tert-octyl-phenyl ether, n = 9 - 10 were identical in the chemical
shift position of their resonances, to differentiate between the spectra the intensity of a
resonance at 3.50 ppm, corresponding to the –(CH2-CH2-O)x – hydrogen atoms were
used. In polyethylene glycol 4-tert-octyl-phenyl ether, n ~ 5 x = 4.5 and in polyethylene
glycol 4-tert-octyl-phenyl ether, n = 9 - 10 x = 9.5. To determine the presence of the
two polyethylene glycol 4-tert-octyl-phenyl ethers the intensity of the resonances not
from the –(CH2-CH2-O)x – hydrogen atoms were compared to those from
–(CH2-CH2-O)x –.
No resonances were present in the PS + additives sample that were not observed in
the standard compounds, the PS without additives or the solvent blank.

As with previous extracts it can clearly be seen that differences exist between the
extracts of the PET + additives, the PET control and the solvent blank (Figure 75). By
comparing the spectra of the additives it can be seen that 2-(2H-benzotriazole-2-yl)-
4,6-bis(1-methyl-1-phenylethyl)phenol is present in the PET extract observed (Figure
76), no resonances relating to the other two additives were observed. The remaining
two additives were found to be virtually insoluble in the extraction solvent and as such
were present at too low a concentration to be detected. Several resonances were
observed in the spectra that do not originate from the additives, solvent or plastic;
Figure 77 highlights three of these regions.
- 79 -
The extract of the PVC polymer containing additives produced highly intense spectra.
Five of the six of the additives used in the PVC were detected, ESBO, dioctyltin
bis(ethylmaleate), dioctyltin bis(2-ethylhexyl thioglycolate), stearic acid and ATBC. The
paraffin wax was not detected. Comparison of the spectra for the PVC extracts shows
a very distinct difference between the PVC samples with and without additives (Figure
78). The NMR spectra of the additives are compared with the PVC with and without
additives in Figure 79. The compounds relating to the extra resonances in the extracts
of the additive standards were identified by comparison of their 1D spectra.
Resonances were observed in the ATBC standard that could not be assigned to this
molecule and were therefore concluded to be derived from impurities present in this
standard. The intensities of these resonances were approximately 250X less than the
intensity of the peak at 3.18 ppm. The resonances were also observed in the PVC with
additives sample but not in the PVC without additives or solvent blank samples. These
resonances are displayed in Figure 80.
6.5.6 Polyamide
Neither of the PA additives could be analysed by NMR. Figure 81 shows spectra of
both the plastic blank extract and the PA + additive extract. These spectra are identical
indicating that none of the zinc stearate additive was extracted nor any reaction and
breakdown products. Talc is aprotic and therefore could not be detected.
6.5.7 2-Dimensional NMR

Although reaction and breakdown products could be observed in the 1-dimensional
NMR spectra of the polymer + additive extracts the identities of the substances giving
rise to these resonances could not be determined. Although not within the original
project scope further work was carried out to analyse the PP extracts using
2-dimensional NMR.
Analysis of the 1H 1D NMR spectra generated for the PP analysis had determined the
presence of impurities in the PP with additives sample at the chemical shift ranges
δ = 4.25 – 4.30, 4.42 – 4.54 and 4.79 – 4.83 ppm. 2D NMR techniques were utilised to
determine further structural information about the non-assigned impurities present. 2D
NMR techniques were employed as they provide extra information about the hydrogen
atoms that cannot be obtained from the 1H 1D NMR spectrum. The 2D NMR
13
techniques utilised were C – 1H Heteronuclear Single Quantum Correlation (HSQC)
spectroscopy and 1H – 1H Total Correlation Spectroscopy (TOCSY).
- 80 -
1
H – 1H TOCSY is a NMR spectroscopy technique that generates a 2D contour map
with the 1H chemical shift represented on both axes. The 1H 1D NMR spectrum is
represented as a contour plot diagonally from the lower left to the upper right of the
spectrum. Peaks that are part of the same spin system (peaks from 1H atoms that are
connected through J coupling interactions) will show off-diagonal peaks that connect
the diagonal peaks by horizontal and vertical lines. By utilising these connectivity’s,
peaks can be connected to aid molecule assignment.
HSQC is a NMR spectroscopy technique that generates a 2D contour map with the
axes 1H chemical shift and 13C chemical shift. 1H atoms directly attached to a 13C atom
(1.1% of all carbon) are shown as contours at positions corresponding to the 1H
chemical shift of the 1H atom and the 13
C chemical shift of the 13
C atom. 13
C – 1H
HSQC spectra were used to resolve peaks that overlap in the 1H 1D NMR spectrum
13
and to determine information about the chemical environment of the C nucleus
observed.
1
H – 1H TOCSY and 13
C – 1H HSQC NMR spectra were acquired on the following
samples; PP + additives, PP without additives, erucamide, poly(4-hydroxy-2,2,6,6-
tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid), tris(2,4-di-tert-
butylphenyl)phosphite, diparamethyldibenzylidene sorbitol, glycerol monostearate, and
pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
The resonances that were assigned to breakdown / impurity products in the PP

containing additives sample were identified in the 1H – 1H TOCSY NMR spectrum
(Figure 82). To determine which resonances observed in the 1H – 1H TOCSY were
from unidentified impurity peaks an overlay plot of the PP without additives,
poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid),
diparamethyldibenzylidene sorbitol, pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate) and glycerol monostearate was generated (Figure 83) and
compared to Figure 82. These standards were chosen as they had shown resonances
in the region 2.5 – 5 ppm. Several off-diagonal crosspeaks were observed which were
not present in either the PP + additive extracts or the standards.
Examination of the 1H – 1H TOCSY spectra enabled several conclusions to be drawn:

• The peaks identified in the 1H 1D NMR spectrum at the central chemical shifts
of 4.80, 4.52, 4.46 were part of the same spin system and hence part of the
same molecule. They were also connected to a resonance at 3.74 ppm which
- 81 -
had not been previously identified as an impurity resonance. Examination of
the region 3.7 – 3.8 ppm in the 1H 1D NMR spectra showed that in this region
there was significant overlap with the resonances of identified additive
compounds. This overlap had obscured the identification of the impurity
resonance at 3.74 ppm.
• The resonance identified as an impurity resonance at the central chemical shift

at 4.27 ppm did not show any observable 1H – 1H TOCSY correlations. The
shape of this peak would suggest that it is part of a larger spin system so it is
hypothesised that these cross peaks are obscured by other cross peaks.
• The resonances assigned to the additive glycerol monostearate displayed off-

diagonal crosspeaks not observed in the standard compound. It is
hypothesised that some of the glycerol monostearate compound within the
plastic had undergone degradation. This breakdown product would contain the
same core structure of glycerol monostearate (corresponding to the overlapping
resonances at 4.25, 4.18, 4.06 and 3.94 ppm).
• There are significantly more off-diagonal crosspeaks observed in the PP with

additives sample when compared to the over plot of the same region of the
standard compounds acquired in Figure 83. These results are highlighted in
Figure 84.
13
C – 1H HSQC analysis of the PP containing additives sample was completed
following the same rationale of examining the region of the 1H 1D NMR spectra where
13
the non-assigned impurities were observed. The C – 1H HSQC spectrum of PP
containing additives is shown in Figure 85. To determine which resonances observed
13
in the C – 1H HSQC spectrum were from unidentified peaks an overlay plot of the PP
without additives, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-
butanedioic acid), diparamethyldibenzylidene sorbitol, pentaerythritol tetrakis(3,5-di-
tert-butyl-4-hydroxyhydrocinnamate)and glycerol monostearate was generated (Figure
86) and compared to Figure 85. Again these standards were chosen as they had
13
shown resonances in the region 2.5 – 5 ppm. Examination of the C – 1H HSQC
spectra acquired revealed several resonances that were not observed in the PP
without additives or the standard compounds. These resonances are highlighted in
Figure 87.
- 82 -
Further analysis of the 2D NMR data acquired was not carried out. The complexity of
the NMR spectra obtained in both 1 and 2 dimensions with many overlapping
resonances meant that additional information could not be derived within the timeframe
and budget of this study. The results generated demonstrated the utility of NMR
spectroscopy in the area of detection of impurities and reaction and breakdown
products in plastics. Further analysis on the 1H – 1H TOCSY spin systems observed
13 13
and the C information observed in the C – 1H HSQC spectrum would aid structural
elucidation of these compounds. Further spectroscopic analysis including the
acquisition of other multi-dimensional NMR utilising the information inherent in the
NMR spectra would also aid in the assignment of these impurities.
7. MIGRATION MODELLING
The estimated concentrations of the impurities, reaction products and breakdown
products are described in Section 6. From these concentrations the worst case
migration was calculated. This calculation applies the convention that 1 kg of food is
packaged in 6 dm2 of plastic and that all of the substance present in the plastic
transfers to the foodstuff. This will be a large overestimation for some
plastic/substance combinations. Therefore to assess the significance of the levels
detected in the polymers migration modelling was applied. Migration modelling was
carried out according to the procedure described in Directive 2002/72/EC and in the
Practical Guide using the commercially available software package Migratest © Lite
which was kindly provided by FABES. Other software packages are available,
including SMEWISE (INRA) and EXDIF v 1.0 (Swiss Federal Office of Public Health).
All are essentially based on diffusion theory and consideration of partitioning effects.
The underlying key parameters are the diffusion coefficient of the migrant in the plastic
(DP) as well as the partition coefficient of the migrant between the plastic and the
food(simulant) KP,F. These models have been shown to provide an estimation of worse
case migration (not total transfer) and are designed such that they predict the migration
that will occur with sufficient safety margins. The application of these generally
recognised migration models to demonstrate compliance with SML’s is permitted in the
latest version of the Plastics Directive (2002/72/EC, as amended). The concentration
of a substance that would need to be present in the plastic to result in a migration of
10 µg/kg (generally defined as the concentration in the food at which a non-permitted
ingredient should be not detectable, this is used for non-CMR substances
(carcinogens, mutagens and reprotoxins) and does not imply a threshold of concern)
was calculated for the PP, HDPE, PS and PET polymers (Table 40). This
- 83 -
concentration was selected as a defining parameter because the identities, and
therefore the toxicity, of many of the impurities, reaction products and breakdown
products are not known. As the contact conditions for these non-food contact polymers
prepared specifically for this project are not defined then exposure conditions of 10
days at 40°C were selected. It was also assumed th at the modelled substance is
soluble in the food (simulant). The migration from PVC could not be modelled as the
polymer specific constant and the associated diffusion coefficient are not defined for
this polymer. As discussed in Section 6.2.2.5 the estimated concentrations of many of
the impurities/reaction/breakdown products detected in the extracts were high up to
204 mg/dm2. Assuming total transfer from the polymer to any foodstuff with which it
comes into contact the migration potential is up to1225 mg/kg. The migration from the
PA was not modelled as no additional peaks were detected in the extracts of the PA +
additive samples that were not present in the PA control samples.
For the PP any 100 Da substances present at concentrations in excess of 4 µg/dm2,

any 500 Da substances present at concentrations in excess of 33 µg/dm2 and any
1000 Da substances present at concentrations in excess of 189 µg/dm2 would have a
migration potential greater than 10 µg/kg. Clearly many of the substances detected in
the PP + additive samples were estimated to be in excess of these concentrations.
For the HDPE any 100 Da substances present at concentrations in excess of 2 µg/dm2,
any 500 Da substances present at concentrations in excess of 17 µg/dm2 and any
1000 Da substances present at concentrations in excess of 95 µg/dm2 would have a
migration potential greater than 10 µg/kg. Again many of the substances detected in
the HDPE + additive samples were estimated to be in excess of these concentrations.
For the PS none of the substances detected in the extracts were present at
concentrations that would result in a migration in excess of 10 µg/kg. The highest
estimated concentration of any of the peaks detected in the plastic, including the
additives, was 80 µg/dm2. Therefore although impurities, reaction and breakdown
products were detected they were not estimated to be present at levels that would
result in migration above a concentration of 10 µg/kg.
For the PET only one reaction/breakdown product was detected by GC-MS with an
estimated concentration of 245 µg/dm2. The ions obtained in the mass spectrum of this
unknown reveal that the mass of this substance is at least 246 Da. Modelling the
- 84 -
migration specifically for this mass and concentration in the PET gives a worst case
migration after exposure for 10 days at 40°C of les s than 10 µg/kg.
8. CONCLUSIONS
8.1 Summary of findings
From the main theoretical chemical reaction pathways and literature searches,
impurities, reaction and breakdown products were predicted for each test polymer.
Analysis of the starting substances as well as the six test polymers with and without
additives has detected numerous impurities and reaction and breakdown products.
8.1.1 Polypropylene
71 substances/classes of substances predicted from the main theoretical chemical
reaction pathways and literature searches. The table below summarises the
substances detected in the PP + additive samples that were not present in the PP only
control samples:
Thermodesorption 0 substances detected

GC-MS
Solvent extraction 55 substances detected 3 additives

GC-MS
17 impurities
- identities proposed for 12
- 5 predicted
35 reaction/breakdown products
- 5 predicted
Solvent extraction 23 additional substances 0 additives

GCxGC-MS detected (i.e. not seen by
12 derived from standards
GC-MS)
- 4 predicted
- 0 predicted

LC-MS and LC-FT-MS
1 impurity
- 1 predicted
- 85 -
- 6 predicted

substances detected in the HDPE + additive samples that were not present in the
HDPE only control samples:
Thermodesorption 2 substances detected 2 reaction/breakdown products

GC-MS - identities proposed for 2
- 0 predicted

GC-MS
29 impurities
- 3 predicted
- 12 predicted
Solvent extraction 0 additional substances

GC-MS)

LC-TOF-MS
6 impurities
- 0 predicted
- 2 predicted
8.1.3 Polystyrene
substances detected in the PS + additive samples that were not present in the PS only
control samples:

GC-MS

GC-MS
14 impurities
- 86 -
- 3 predicted
- 0 predicted

GC-MS)

LC-MS and LC-FT-MS
- 1 predicted

substances detected in the PET + additive samples that were not present in the PET
only control samples:

GC-MS
Solvent extraction 2 substances detected 1 additive

GC-MS
1 reaction/breakdown product
- 0 predicted

GC-MS)
Solvent extraction 3 substances detected 1 additive

LC-MS and LC-FT-MS
- 0 predicted

substances detected in the PVC + additive samples that were not present in the PVC
only control samples:
- 87 -
Thermodesorption 3 substances detected 3 reaction/breakdown products
GC-MS - identities proposed for 3
- 3 predicted
Solvent extraction 145 substances detected* 1 additive

GC-MS
25 impurities
- 2 predicted
- 2 predicted
Solvent extraction Not analysed

GCxGC-MS

LC-TOF-MS
5 impurities
- 0 predicted
- 0 predicted
* Does not include alkanes derived from the paraffin wax,
8.1.6 Polyamide
reaction pathways and literature searches. No substances were detected in the PA +
additive samples that were not present in the PA only control samples.
8.1.7 Migration potential of the NIAS

For the PS and PET polymers although NIAS were detected they were not present at
levels that could result in migration above a concentration of 10 µg/kg. PP, HDPE and
PVC contained the most NIAS. Many of these substances were not predicted. Since
these plastics have relatively high diffusivity (the PVC was plasticised) then they
release migrants more readily. Consequently not only did these plastics contain the
most numerous NIAS but these plastics also had the most NIAS with the potential to
migrate into a foodstuff at levels in excess of 10 µg/kg. As the identities of many of the
NIAS are not known then this concentration was selected as it is generally defined as
the concentration in the food at which a non-permitted ingredient should be not
detectable.
- 88 -
8.2 Additive purity and the impact on NIAS
There were many unexpected impurities in the additives themselves. Although each
additive may have been of good technical quality, this finding does illustrate the
demands placed when considering migration potential at the very low level of parts-per-
billion (µg/kg). These impurities have the potential to persist in the finished plastic food
contact material and may migrate. Furthermore, they may decompose under the
plastic process and fabrication conditions or they may interact one with another to form
other substances, all with the potential to migrate. This work started with a literature
search and a prediction from chemical principles on what reaction and breakdown
products may be anticipated based on consideration of only the named additive listed
in the formulation. Given that some of the additives contained more than 10 different
substances and that there may be several additives in any one plastic then the list of
potential NIAS is large.
8.3 Limitation on predictions of reaction and breakdown products as NIAS

When considering the likely reactions of known ingredients, only the main reaction
pathways were considered. There are many other chemical reactions and
transformations possible – indeed the possibilities are almost endless, but they do not
come to mind because perhaps they are energetically very unfavourable or
mechanistically improbable. Again however, when the level of interest is a migration
potential at the very low level of parts-per-billion then even the unfavourable or the
improbable may come into play. A reaction pathway with only 0.01% yield will still form
50 ppb from an additive used at 500 ppm. When a NIAS is identified, the precursors
and the reaction mechanism may be rationalised post-event but it is unlikely that many
or most can be predicted ahead of time based only on first principles and text-book
chemistry.
8.4 Limitations of analytical methods to detect, identify and measure NIAS

This project represents the state-of-the-art with two highly experienced and well-
equipped institutes bringing their combined resources to bear on this question. A
number of substances that can be categorised as NIAS have been identified.
However, a larger number of substances remain either unidentified or with an
ambiguous identification only. It can be concluded that for surveillance and official
enforcement laboratories this will be the situation too – the full elucidation of all NIAS
cannot be achieved using analytical chemistry alone.
- 89 -
It is certain that the responsible chemical and plastics industries could identify some
more of these substances by using their scientific and technical know-how built-up over
many years. This notwithstanding, within a reasonable resource and time allocation
the combination of theoretical predictions with the application of advanced analytical
techniques is unlikely to be capable of detecting and identifying every non-intentionally
added substance in food contact plastics.
8.5 Other assessment techniques that may be considered

If NIAS are known or if they become identified and shown to migrate then any hazard
they may present has to be assessed. Approaches that may be considered to achieve
this at reasonable cost and avoiding unwanted use of animals, include the use of
estimates of exposure and QSAR modelling of toxicity.
If NIAS escape detection (which is likely) or if they are detected but defy identification
(which is also likely), then it seems probable that the analytical chemistry approach
used here may need to be linked with complementary approaches. If achievable, such
an approach worth considering would be the toxicological evaluation of the whole
migrate and/or threshold concepts such as threshold of regulation or thresholds of
toxicological concern which are concepts advocated elsewhere. All of these would
have to be assessed by European Authorities to ensure the resulting method is
appropriate, scientifically sound and reliable.
9. REFERENCES
[1] Opinion of the Scientific Panel on Food Additives, Flavourings, Processing Aids
and Materials in Contact with Food (AFC) on a request from the Commission
related to the use of Epoxidised soybean oil in food contact materials. 26 May
2004.
[2] Advice of the ad hoc expert group set up to advise the European Food Safety
Authority (EFSA) on the possible occurrence of semicarbazide in packaged
foods. 28 July 2003.
[3] FSA Project A03037. LC-MS method development for the screening of non-
volatile and polar compounds present in paper and board or plastic food contact
materials and articles: Testing for semicarbazide without derivatisation or acid
hydrolysis: Final report. W. A. Read, L. Castle, L. Coulier, E. K. Zondervan-van
Beuken & M. A. H. Rijk. December 2003.
- 90 -
[4] R. H. Stadler, P. Mottier, P. Guy, E. Gremaud, N. Varga, S. Lalljie, R. Whitaker,
J. Kintscher, V. Dudler, W. A. Read and L. Castle. The Analyst, 2004, 129,
276.
[5] R. Beswick and D. Dunn, 2002. Plastics in Packaging - Western Europe and
North America. Market Report 2002.
[6] H. H. Kausch, Macromol. Symp. 225 (2005) 165.
[7] J. C. W. Chien, in: Degradation and Stabilisation of Polymers, G. Geuskens,
Applied Science Publ., London, 1975, 95.
[8] G. Geuskens, M. S. Kabamba, Polymer Degradation and Stability, 1982, 4, 69;
1983, 5, 399.
[9] R. Buchalla, C. Boess, K. W. Bogl, Applied Radiation and Isotopes, 2000, 52,
251.
[10] T. L. Smith, D. Masilamani, L. K. Bui, Y. P. Khanna, R. G. Bray, W. B.
Hammond, S. Curran, J. J. Belles Jr. and S. Binder-Castelli, Macromolecules,
1994, 27, 3147.
[11] US Patent 5198484
[12] European Patent EP-A-451 002
[13] N. Haider and S. Karlsson, Journal of Applied Polymer Science, 2002, 85, 974.
[14] A. Feigenbaum, D. Scholler, J. Bouqant, G. Brigot, D. Ferrier, R. Franz, L.
Lillemark, A. M. Riquet, J.H. Petersen, B. van Lierop and N. Yagoubi, Food
Additives and Contaminants, 2002, 19, 184.
[15] Handbook of Polymer Degradation, 2nd Ed., 2000, S. Halim Hamid (ed.), Marcel
Dekker Inc., NY, USA.
[16] F. Bourges, G. Bureau, J. Dumonceau and B. Pascat, Packaging Technology
and Science, 1992, 5, 205.
[17] F. Bourges, G. Bureau and B. Pascat, Food Additives and Contaminants, 1993,
10, 443.
[18] P. G. Demertzis, R. Franz and F. Welle, Packaging Technology and Science,
1999, 12, 119.
[19] K. A. Riganakos, W. D. Koller, D. A. E. Ehlermann, B. Bauer and M. G.
Kontominas, Radiation Physics and Chemistry, 1999, 54, 527.
[20] F. C.-Y. Wang, Journal of Chromatography A, 2000, 891, 325.
[21] J. Pospisil, Advances in Polymer Science, 1980, 36, 69.
[22] J. Pospisil, Polymer Degradation and Stability, 1993, 40, 217.
[23] J. Pospisil, Polymer Degradation and Stability, 1991, 34, 85.
[24] I. Skjevrak, C. Brede, I.-L. Steffensen, A. Mikalsen, J. Alexander, P. Fjeldal and
H. Herikstad, Food Additives and Contaminants, 2005, 22, 1012.
- 91 -
[25] D. Brocca, E. Arvin and H. Mosbaek, Water Research, 2002, 36, 3675.
[26] D. Dilettato, P.J. Arpino, K. Nguyen, A. Bruchet, Journal of High Resolutuion
Chromatography, 1981, 14, 335.
[27] N. Haider and S. Karlsson, Polymer Degradation and Stability, 2001, 74, 103.
[28] K. Kimura, T. Yoshikawa, Y. Taguchi, Y. Ishida, H. Ohtani and S. Tsuge,
Analyst, 2005, 125, 465.
[29] M. Blaszo, Journal of Analytical and Applied Pyrolysis, 2001, 58-59, 29.
[30] J. Pospisil, Advances in Polymer Science, 1995, 124, 87.
[31] P. Jiang-Qing and C. Song, Polymer Degradation and Stability, 1993, 40, 375.
[32] US Patent 3926523, 1975
[33] US Patent 3006934, 1964
[34] S. W. Bigger, M. J. O'Connor, J. Schreirs, J. L. G. M. Janssens, J. P. H. Linssen
and A. Legger-Huysman, in Polymer Durability. Eds. R.L. Clough, N.C.
Billingham and K.T. Gillen, ACS, Washington, 1996, 249.
[35] C. W. Peloso, M. J. O'Connor, S. W. Bigger and J. Schreirs, Polymer
Degradation and Stability, 1998, 62, 285.
[36] C. A. Shuler, A. V. Janorkar and D. E. Hirt, Polymer Engineering and Science,
2004, 44, 2247.
[37] C. C. Yu, Y.-S. Lee, B. S. Cheon and S. H. Lee, Bulletin of the Korean
Chemical Society, 2003, 24, 1229.
[38] W. Camacho and S. Karlsson, Polymer Degradation and Stability, 2000, 71,
123.
[39] G. Demertzis and R. Franz, Food Additives and Contaminants, 1998, 15, 93.
[40] J. Scheirs, J. Pospisil, M. J. O'Connor and S. W. Bigger, Characterization of
conversion products formed during degradation of processing antioxidants.
American Chemical Society, Washington, 1996.
[41] L. Deschenes, D. J. Carlsson, Y. Wang and C. Labreche, Irradiation of Food
and Packaging: Recent Developments, 2004, 875, 277.
[42] M. S. D. Garcia, J. M. Lopez, R. Bouza, M. J. Abad, E. G. Soto and M. V. G.
Rodriguez, Analytica Chimica Acta, 2004, 521, 179.
[43] C. Strandberg and A. C. Albertsson, Journal of Applied Polymer Science, 2005,
98, 2427.
[44] N. H. Stoffers, J. P. H. Linssen, R. Franz and F. Welle, Radiation Physics and
Chemistry, 2004, 71, 205.
[45] R. Buchalla, C. Schuttler and K. W. Bogl, Journal of Food Protection, 1993, 56,
998.
[46] N. S. Allen and H. Katami, Polymer Degradation and Stability, 1996, 52, 311.
- 92 -
[47] N. S. Allen, M. Edge, T. Corrales and F. Catalina, Polymer Degradation and
Stability, 1998, 61, 139.
[48] N. S. Allen, H. Khatami and F. Thompson, European Polymer Journal, 1992,
28, 817.
[49] N. S. Allen and H. Katami, Polymer Durability, 1996, 249, 537.
[50] N. S. Allen, M. Edge, A. Ortega, G. Sandoval, C. M. Liauw, J. Verran, J.
Stratton and R. B. McIntyre, Polymer Degradation and Stability, 2004, 85, 927.
[51] N. S. Allen, M. Edge, T. Corrales, A. Childs, C. M. Liauw, F. Catalina, C.
Peinado, A. Minihan and D. Aldcroft, Polymer Degradation and Stability, 1998,
61, 183.
[52] H. Djidjelli and D. Benachour, Macromolecular Symposia, 1998, 127, 181.
[53] F. Vilaplana, A. Ribes-Greus, S. Karlsson, Polymer Degradation and Stability,
2006, 91, 2163.
[54] J. Hacaloglu, T. Ersen, N. Ertugrul, M. M. Fares and S. Suzer, European
Polymer Journal, 1997, 33, 199.
[55] G. N. Ghebremeskel, J. K. Sekinger, J. L. Hoffpauir and C. Hendrix, Rubber
Chemistry and Technology, 1997, 69, 874.
[56] R. P. Singh, S. M. Desai, S. S. Solansky and P. N. Thanki, Journal of Applied
Polymer Science, 2000, 75, 1103.
[57] R. Buchalla, T. H. Begley and K. M. Morehouse, Radiation Physics and
Chemistry, 2002, 63, 837.
[58] S. R. Howe, P. Surana, M. R. Jakupca and L. Borodinsky, Food Additives and
Contaminants, 2001, 18, 1021.
[59] J. Ejlertsson and B. H. Svensson, Biodegradation, 1996, 7, 501.
[60] M. C. Pietrogrande, D. Rossi and G. Paganetto, Analytica Chimica Acta, 2003,
460, 1.
[61] F. C.-Y. Wang, Journal of Chromatography A, 2000, 883, 199.
[62] H.-J. Chen, D.-H. Tseng and S.-L. Huang, Bioresearch Technology, 2005, 96,
1483.
[63] M. A. Darth, T. J. Korniski and J. l. Gerlock, Polymer Degradation and Stability,
1995, 48, 111.
[64] J. E. Pickett, ACS Symposium Series, 2002, 805, 250.
[65] S. Al-AbdulRazzak and S .A. Jabarin, Polymer International, 2002, 51, 164.
[66] H. A. Pohl, Journal of the American Chemical Society, 1951, 73, 5660.
[67] D. N. Bikiaris and G. P. Karayannidis, Polymer Degradation and Stability, 1999,
63, 213.
[68] W. A. MacDonald, Polymer International, 2002, 51, 923.
- 93 -
[69] C. F. L. Ciolacu, N. R. Choudhury and N. K. Dutta, Polymer Degradation and
Stability, 2006, 91, 875.
[70] G. J. M. Fechine, M. S. Rabello and R. M. Souto-Maior, Polymer Degradation
and Stability, 2002, 75, 153.
[71] N. Torres, J. J. Robin and B. Boutevin, Journal of Applied Polymer Science,
2001, 79, 1816.
[72] B. J. Holland and J. N. Hay, Polymer, 2002, 43, 1835.
[73] S. R. Shukla, E. A. Lofgren and S. A. Jabarin, Polymer International, 2005, 54,
946.
[74] C. Nerin, E. Asensio, C. Fernandez and R. Batlle, Quimica Analitica, 2000, 19,
205.
[75] G. Botelho, A. Queiros, S. Liberal and P. Gijsman, Polymer Degradation and
Stability, 2001, 74, 39.
[76] M. T. de A. Freire, A. P. Damant, L. Castle and F. G. R. Reyes, Packaging
Technology and Science, 1999, 12, 29.
[77] S. Weidner, G. Kuehn, B. Werthmann, H. Schroeder, U. Just, R. Borowski, R.
Decker, B. Schwarz, I. Schmuecking and I. Seifert, Journal of Polymer Science
A: Polymer Chemistry, 1997, 35, 2183.
[78] F. Samperi, C. Puglisi, R. Alicata and G. Montaudo, Polymer Degradation and
Stability, 2004, 83, 3.
[79] M. T. de A. Freire, L. Castle, F. G. R. Reyes and A. P. Damant, Food Additives
and Contaminants, 1998, 15, 473.
[80] J. M. Gramshaw, H. J. Vandenburg and R. A. Lakin, Food Additives and
[81] M. Kashtock and C. N. Breder, Journal of the Association of Official Analytical
Chemists, 1980, 63, 168.
[82] T. H. Begley and H. C. Hollifield, Journal of Food Protection, 1990, 53, 1062.
[83] L. Castle, A. Mayo, C. Crews and J. Gilbert, Journal of Food Protection, 1989,
52, 337.
[84] T. H. Begley, J. L. Denninson and H.C. Hollifield, Food Additives and
[85] F. Buiarelli, G. Cartoni and F. Coccioli, Annali di Chimica, 1993, 83, 93.
[86] C. H. Do, E. M. Pearce, B. Bulkin and H. K. Reinschuessel, Journal of Polymer
Science Polymer Chemistry Edition, 1986, 24, 1657.
[87] C. H. Do, E. M. Pearce and H.K. Reinschuessel, Journal of Polymer Science
Polymer Chemistry Edition, 1987, 25, 2301.
[88] H. D. Scharf, Angewandte Makromolekulare Chemie, 1979, 79, 193.
- 94 -
[89] P. M. Subramanian and V. Mehra, Polymer Engineering and Science, 1989, 27,
663.
[90] P. Rajagopalan, J.-S. Lim, H. P. Brack, X. Lu, A. Eisenberg, R and A. Weiss,
Journal of Polymer Science Polymer Physics Edition, 1995, 33, 6942.
[91] E. T. Bell, J. R. Bradley, T. E. Long and S. L. Stafford, US Patent 6239233B1,
2001.
[92] S. Bandi, S. Mehta and D. A. Schiraldi, Polymer Degradation and Stability,
2005, 88, 341.
[93] N. S. Allen, J. F. McKellar and G. O. Phillips, Journal of Polymer Science
Polymer Chemistry Edition, 1975, 13, 2857.
[94] K. Lonsdale, Proceedings of the Royal Society London Series A, 1937, 159,
149.
[95] B. N. Achar, G. M. Fohlen, K. S. Lokesh and T. M. Mohan Kumar, International
Journal of Mass Spectrometry, 2005, 243, 199.
[96] V. H. Tran, Journal of Macromolecular Science-Reviews in Macromolecular
Chemistry and Physics C38, 1998, 1.
[97] V. H. Tran, T. P. Nguyen and P. Molinie, Polymer Degradation and Stability,
1996, 53, 279.
[98] W. H. Starnes Jr., Progress in Polymer Science, 2002, 27, 121.
[99] E. Arkis and D. Balkose, Polymer Degradation and Stability, 2005, 88, 46.
[100] D. Atek and N. Belhaneche-Bensemra, European Polymer Journal, 2005, 41,
707.
[101] I. Mersiowsky, R. Stegmann and J. Ejlertsson, Plastics Rubber and
Composites, 1999, 28, 321.
[102] H. Bockhorn, A. Hornung, U. Hornung, S. Teepe and J. Weichmann,
Combustion Science and Technology, 1996, 116, 129.
[103] M. Groning and M. Hakkarainen, Journal of Chromatography A, 2004, 1052, 61.
[104] M. Groning and M. Hakkarainen, Journal of Chromatography A, 2004, 1052,
151.
[105] M. Groning and M. Hakkarainen, Journal of Applied Polymer Science, 2002, 86,
3396.
[106] S. V. Levchik, E. D. Weil and M. Lewin, Polymer International, 1999, 48, 532.
[107] D. D. Steppan, M. F. Doherty and M. F. Malone, Journal of Applied Polymer
Science, 1991, 42, 1009.
[108] The EFSA Journal, 2004, 102,1.
[109] B. Andricic and T. Kovacic, Polymer Degradation and Stability, 1999, 65, 59.
[110] Michel, A. and van Hoang, T., Pure and Applied Chemistry, 1981, 53, 567.
- 95 -
[111] Biswas, A., Adhvaryu, A., Gordon, S. H., Erhan, S. Z. and Willett, J. L. Journal
of Agricultural and Food Chemistry, 2005, 53, 9485.
[112] J. Michal, Fire and Materials, 1982, 6, 13.
[113] H. Soto-Valdez and J. W. Gramshaw, Journal of Materials Science Letters,
2000, 19, 823.
- 96 -
Table 1. Formulation details of the PP test material
CAS number Use Level (wt %) Purity

PP Base polymer 65.4
Diparamethyldibenzylidene sorbitol 81541-12-0 Nucleating agent 0.5 Not given
Tris(2,4-di-tert-butylphenyl)phosphite 31570-04-4 Antioxidant 0.5 98%
Pentaerythritol tetrakis(3,5-di-tert-butyl-4-
6683-19-8 Antioxidant 0.5 98%
hydroxyhydrocinnamate)
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-
[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-
71878-19-8 Light stabiliser 1.0 Not given
[(2,2,6,6-tetramethyl-4-piperidinyl)imino]],
Mn ca. 2000
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-
65447-77-0 Light stabiliser 1.0 Not given
butanedioic acid), Mn ca. 3500
Erucamide 112-84-5 Slip agent 0.1 > 97%
Glycerol monostearate 31566-31-1 Anti-static agent 1.0 90+%
Calcium carbonate 471-34-1 Filler 30 99+%
- 97 -
Table 2. Formulation details of the HDPE test material

HDPE Base polymer 92.35
Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-
119345-01-6 Antioxidant 0.1 Not given
diylphosphonite
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate 2082-79-3 Antioxidant 0.1 99%
Oleamide 301-02-0 Slip agent 0.1 Not given
Titanium dioxide 13463-67-7 Inorganic colourant 5.0 99+%
N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine 61791-14-8 Antistatic agent 0.25 Not given
40%,
Glycerol monooleate 111-03-5 Lubricant 1.0 diglyceride 20-40%
triglyceride 20-40%
Sodium (C10-C18) alkyl sulfonate 68037-49-0 Lubricant 1.0 Not given
2,5-Bis(5'-tert.butylbenzoxazol-2-yl)thiophene 7128-64-5 Optical brightener 0.1 Not given
- 98 -
Table 3. Formulation details of the PS test material

PS Base polymer 97.45
Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-
36443-68-2 Antioxidant 0.1 Not given
propionate)
Tris(nonylphenyl)phosphite 26523-78-4 Antioxidant 0.1 Not given
Processing
Di-(2-ethylhexyl) phthalate 117-81-7 2.0 97+%
aids/flow promoter
Mould release
N,N-Bis(stearoyl) ethylenediamide 110-30-5 0.1 Not given
agent
Polyethylene glycol 4-tert-octyl-phenyl ether, n~5 9036-19-5 Emulsifier 0.05 Not given
Polyethylene glycol 4-tert-octyl-phenyl ether, n=9-10 9002-93-1 Emulsifier 0.05 Not given
2-(2’-Hydroxy-5’-methylphenyl)benzotriazole 2440-22-4 UV absorber 0.15 Not given
Table 4. Formulation details of the PET test material

PET Base polymer 97.749
2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol 70321-86-7 UV stabilizer 0.25 Not given
Acetaldehyde
Hexanedioic acid polymer with 1,3-benzenedimethanamine 25718-70-1 2.0 Not given
scavenger
Copper phthalocyanine blue 147-14-8 Colourant 0.001 97%
- 99 -
Table 5. Formulation details of the PVC test material

PVC Base polymer 62.2
Dioctyltin bis(ethylmaleate) 68109-88-6 Stabilisers 1.0 > 50%
Dioctyltin bis(2-ethylhexyl thioglycolate) 15571-58-1 Stabilisers 1.0 > 50%
Epoxidised soya bean oil Stabiliser 5.0 Not given
Stearic acid 57-11-4 Emulsifier 0.3 >97%
Acetyl tributyl citrate 77-90-7 Plasticiser 30.0 98+%
Paraffin wax 8002-74-2 Lubricant 0.5 Not given
Table 6. Formulation details of the PA test material

PA Base polymer 94.9
Talc 14807-96-6 Mineral filler 5.0 Not given
Mould release
Zinc stearate 557-05-1 0.1 Not given
agent
- 100 -
Table 7. List of compounds identified in virgin HDPE
Compounds identified in HDPE

Ethylbenzene
o-Xylene
Aromatic hydrocarbons *
m-Xylene
p-Xylene
Undecane
Hexadecane
Heptadecane
Octadecane
Aliphatic hydrocarbons
Branched alkane 1
Tetracosane
Branched alkane 2
Branched alkane 3
1-Octadecene
Branched alkenes 1-Nonadecene
5-Eicosene
6-Dodecanone
Ketones
2-Nonadecanone
* Proposed, by the authors, to be due to breakdown products of the additives present in
the polymers
119
Table 8. Organo-tin compounds present in a commercial PVC foil by Sn Mössbauer
spectroscopy
Organo-tin compound
Oc2Sn(IOTG)2
OcSn(IOTG)3
Oc2SnCl(IOTG)
OcSnCl(IOTG)2
OcSn(IOTG)2(OCOR)
Oc2Sn(OCOR)2
Oc = octyl
IOTG = isooctylthioglycolate
- 101 -
Table 9. Identified degradation products from the thermooxidation of non-recycled PA
6,6.
Compound
Cyclopentanone
2-Methyl-pyridine
Pentanoic acid
Butanamide
2-Ethyl-cyclopentanone
2,4,6-Trimethyl-pyridine
Pentanamide
3-(1-Methylethyl)-pyridine
2-Butyl-pyridine
N,N-Hexamethylenebisformamide
2-Butyl-cyclopentanone
Glutarimide
1-Propyl-2,5-pyrrolidine-dione
2-Pentyl-cyclopentanone
Caprolactam
Azepane-2,7-dione
2-Cyclopentyl-cyclo-pentanone
1-Butyl-2,5-pyrrolidine-dione
1-Bentyl-2,5-pyrrolidine-dione
2-Butyl-3,5-pyrrolidine-dione
- 102 -
Table 10. Proposed impurities/reaction products/breakdown products for the additives
used in the manufacture of the PP test material
Molecular
Polymer/additive
Molecular formula weight
Proposed impurities/reaction/breakdown products
(g/mol)
Polypropylene
alkanes - -
alkenes - -
alcohols - -
2-methylpropan-1-ol C4H10O 74
2,4-dimethylpentan-1-ol C7H16O 116
Diparamethyldibenzylidene sorbitol C22H26O6 386

acetaldehyde C2H4O 44
3,4-dimethylbenzaldehyde C9H10O 134
sorbitol C6H14O6 182
3,4-dimethylbenzylidene sorbitol C15H20O6 260
Tris(2,4-di-tert-butylphenyl)phosphate C24H63PO3 430

tris(2,4-di-tert-butylphenyl)phosphate (oxidised tris(2,4-
C42H63PO4 663
di-tert-butylphenyl)phosphite)
2,4-di-tert-butylphenol C14H22O 206
1,3-di-tert-butyl-benzene C14H22 190
di(2,4-di-tert-butylphenyl)phosphate C28H43PO3 459
2,4-di-tert-butylphenylphosphate C14H23PO3 271
phosphoric acid H3PO4 99
tert-butyl-phenol C10H14O 150
tert-butyl-benzene C10H14 134
phenol C6H6O 94
benzene C6H6 78
- 103 -
Table 10 continued. Proposed impurities/reaction/breakdown products for the additives
used in the manufacture of the PP test material
Molecular
Polymer/additive
(g/mol)
C73H108O12 1177
2,6-di-tert-butylbenzoquinone,
C14H20O2 220
2,6-di-tertbutyl-2,5-cyclohexadiene-1,4-dione
2,6-di-tert-butylphenol C14H22O 206
p-benzoquinone C6H4O2 108
methyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate C18H28O3 292
ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate C19H30O3 306
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid C17H26O3 278
2-ethylhexyl-p-methoxycinnamate C18H26O3 290
3,5-di-tert-butyl-4-hydroxystyrene C16H24O 232
3,5-di-tert-butyl-4-hydroxybenzaldehyde C15H22O2 234
3,5-di-tert-butyl-4-hydroxyacetophenone C16H24O2 248
quinone methide, {2,6-di-tert-butyl-4-(propen-1-oic)-
2,5-cyclohexadien-1-one}acid, cyclohexa-1,4-diene- C17H24O3 276
1,5-bis-tert-butyl-6-on-4-(2-carboxy-ethylidene)
1,3-di-tert-butyl-benzene C14H22 190
quinone methide methyl ester, cyclohexa-1,4-diene-
1,5-bis-tert-butyl-6-on-4-(2-carboxy-ethylidene) methyl C18H26O3 290
ester
phenol C6H6O 94
di-isopropyl-benzene C12H18 162
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-
triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4- Typically
(C35H68N8)n
piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6- 2000
tetramethyl-4-piperidinyl)imino]],
2,2,6,6-tetramethyl-4-piperidinone C9H17NO 155
2,2,6,6-tetramethyl-4-piperidinol C9H19NO 157
aza-2,2,6,6-tetramethyl-3-cyclohexene C9H17N 139
2,2,6,6-tetramethyl-piperidine methyl ether C10H21NO 171
- 104 -
Table 10 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the PP test material
Molecular
Polymer/additive
(g/mol)
2-methyl-2,4-pentadiene C6H10 82
tert-octene C8H16 112
isopropenylamine C3H9N 59
2,6-dimethylpyridine C7H9N 107
2,6-dimethylaniline C8H11N 121
2,6-dimethylbenzene C8H10 106
2,7,7-trimethyl-5-cycloheptene C9H17N 139
2,2,6,6-tetramethyl-4-aminopiperidine C9H20N2 156
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene Typically
(C15H25O4N)n
ethanol-alt-1,4-butanedioic acid) 3500
1-aza-2,2,6,6-tetramethyl-3-cyclohexeneethanol C11H21NO 183
methyl-1-aza-2,2,6,6-tetramethyl-3-cyclohexeneethyl
C16H27NO4 297
succinate
aza-1,2,2,6,6-pentamethyl-3-cyclohexene C10H19N 153
4-hydroxy-1,2,2,6,6-pentamethylpiperidine C10H21NO 171
aza-2,2,6,6-tetramethyl-3-cyclohexene C9H17N 139
trans-2,6-dimethyl-2,4,6-heptatriene C9H14 122
2-methyl-2,4-pentadiene C6H10 82
4-hydroxy-2,2,6,6-tetramethylpiperidine C9H19NO 157
butanedioic acid C4H6O4 118
cis-butanedioic anhydride C4H4O3 100
Erucamide C22H43NO 337

erucyl nitrile C22H41N 319
erucic acid, docosenoic acid C22H41O2 339
nonanal C9H18O 124
13-oxo-tridecanoic acid amide C13H25NO 211
13-hydroxy-cis-14-docosenamide C22H43NO2 353
- 105 -
additives used in the manufacture of the PP test material
Molecular
Polymer/additive
(g/mol)
Glycerol monostearate C21H42O4 358

octadecanoic acid C18H36O2 284
tetradecanoic acid C14H28O2 228
hexadecanoic acid C16H32O2 256
ethyl stearate C20H40O2 313
glycerol C3H8O 92
glycerol distearate C39H76O5 624
glycerol tristearate C57H110O6 890
Calcium carbonate CaCO3 100

calcium oxide CaO 56
calcium hydrogen carbonate CaC2H2O6 162
- 106 -
used in the manufacture of the HDPE test material
Molecular
Polymer/additive
(g/mol)
HDPE
alkanes
alkenes
ketones
diylphosphonite C68H92O4P2 1035
1,1-biphenyl C12H10 154
phenol C6H6O 94
2,4-di-t-butyl phenol C14H21O 205
2,4-bis(1,1-dimethylethyl)phenol C14H22O 206
2-t-butyl phenol C10H14O 150
4-t-butyl phenol C10H14O 150
R
O O R
P P
O H O
C12H12O4P2 282
R R
R R
R = tert-butyl
O H O
P P
O H O
C26H32O4P2 470
R R
R R
R = tert-butyl
- 107 -
additives used in the manufacture of the HDPE test material
Molecular
Polymer/additive
(g/mol)
O H O
P P
HO
H O
C40H52O4P2 658
R
R = tert-butyl
O H O
P P
HO
H OH
C54H72O4P2 846
R = tert-butyl
R R
R O O
P P
O O O
C68H92O5P2 1051
R R
R R
R = tert-butyl
- 108 -
Molecular
Polymer/additive
(g/mol)
R R
R O O O
P P
O O O
C68H92O6P2 1067
R R
R R
R = tert-butyl
phosphorus trichloride PCl3 136
C12H10Cl 189
C12H9Cl2 223
C12H8Cl3 257
C12H7Cl4 291
C12H6Cl5 325
polychlorinated biphenyls C12H5Cl6 359
C12H4Cl7 383
C12H3Cl8 427
C12H2Cl9 461
C12HCl10 495
C12Cl11 529
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate C35H62O3 530

2,6-di-t-butyl phenol C14H21O 205
benzoquinone C6H4O2 108
diphenoquinonone C12H8O2 184
quinone methide C35H59O3 527
cinnammate C35H59O3 527
octadecanol C18H38O 270
cinnamate minus octadecanol C17H23O3 275
quinone methide minus octadecanol C17H23O3 275
t-butylene C4H8 56
- 109 -
Molecular
Polymer/additive
(g/mol)
OH
C27H46O3 418
H37C18
O O
= thermal oxidation product 1
OH
t-Bu
C31H54O3 474
H37C18
O O
= thermal oxidation product 2
thermal oxidation product 1 minus octadecanol C13H18O3 222
thermal oxidation product 2 minus octadecanol C9H10O3 166
Oleamide C18H35NO 281

oleic acid C18H34O2 282
formamide CH3NO 45
acetamide C2H5NO 59
urea CH4N2O 60
acetyl urea C3H6N2O2 102
oleyol chloride C18H33OCl 300
ammonia H3N 17
methyl oleate C19H36O2 296
dihydroxy oleamide C18H39NO3 317
- 110 -
Molecular
Polymer/additive
(g/mol)
Titanium dioxide O2Ti 80
N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C13 C17H37NO2 287

C14 C18H39NO2 301
C15 C19H41NO2 315
ethylene oxide C2H4O 44
primary amine C13 C13H29N 199
secondary amine C13 C15H33NO 243
Glycerol monooleate C21H40O4 356

glycerol C3H8O3 92
phosphoric acid H3O4P 98
dihydroxy oleic acid C18H41O4 321
Sodium (C10-C18) alkyl sulfonate

C10 C10H21O4SNa 260
C11 C11H23O4SNa 274
C12 C12H25O4SNa 288
C13 C13H27O4SNa 302
C14 C14H29O4SNa 316
C15 C15H31O4SNa 330
C16 C16H33O4SNa 344
C17 C17H35O4SNa 358
- 111 -
Molecular
Polymer/additive
(g/mol)
C18 C18H37O4SNa 372

C10 sulphonic acid C10H23O3S 223
2,5-Bis(5'-tert.butylbenzoxazol-2-yl)thiophene C26H26N2O2S 430
- 112 -
used in the manufacture of the PS test material
Molecular
Polymer/additive
(g/mol)
Polystyrene (HIPS)
styrene C8H8 104
styrene dimer C16H17 209
alpha-methylstyrene C9H10 118
styrene trimer C24H25 313
styrene oligomers - -
butadiene C4H6 54
butadiene oligomers - -
1-phenylethanol C8H10O 122
acetophenone C8H8O 120
benzaldehyde C7H6O 106
phenol C6H6O 94
ethylbenzene C8H10 106.
Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-
hydroxy-m-tolyl)-propionate) C34H50O8 587
2-tert-butyl-6-methyl-benzoquinone C11H14O2 178
2-tert-butyl-6-methyl-phenol C11H16O 164
phenol C6H6O 94
methylphenol C7H8O 108
3-methyl-5-tert-butyl-4-hydroxy styrene C13H18O 190
3-methyl-5-tert-butyl-4-hydroxy benzaldehyde C12H16O2 192
3-methyl-5-tert-butyl-4-hydroxy acetophenone C13H18O2 206
(2-methyl-6-tert-butyl-4-(propen-1-oic)-2,5-
cyclohexadiene-1-one) acid C14H18O3 234
3-methyl-5-tert-butyl-4-hydroxyphenyl
methylpropanoate C15H22O3 250
3-methyl-5-tert-butyl-4-hydroxyphenyl ethylpropanoate C16H24O3 264
3-methyl-5-tert-butyl-4-hydroxyphenyl propanoic acid C14H20O3 236
- 113 -
additives used in the manufacture of the PS test material
Molecular
Polymer/additive
(g/mol)
TNPP C45H69O3P 689

nonylphenol C15H24O 220
tris(nonylphenyl)phosphate C45H69O4P 704
di(nonylphenyl)phosphite C30H47O3P 486
di(nonylphenyl)phosphate C30H47O4P 502
(nonylphenyl)phosphite C15H25O3P 284
(nonylphenyl)phosphate C15H25O4P 300
phenol C6H6O 94
nonane C9H20 128
nonene C9H18 126
DEHP C24H38O4 391

MEHP C16H23O4 279
2-ethylhexanol C8H18O 130
octanol C8H18O 130
dimethylphthalate C10H10O4 178
2-ethylhexyl aldehyde C8H17O 129
2-ethylhexanoic acid C8H16O2 144
phthalic acid C8H6O4 166
N,N-Bis(stearoyl)ethylenediamide C38H76N2O2 593

octadecanoic acid C18H36O2 285
octadecanamide C18H37ON 284
Polyethylene glycol 4-tert-octyl-phenyl ether, n~5

and Polyethylene glycol 4-tert-octyl-phenyl ether, 426-646
n=9-10
octylphenol C14H22O 206
octylphenol ethoxylates oligomers - -
- 114 -
additives used in the manufacture of the PS test material
Molecular
Polymer/additive
(g/mol)
2-(2’-Hydroxy-5’-methylphenyl)benzotriazole C13H11N3O 225

benzotriazole C6H5N3 119
- 115 -
used in the manufacture of the PET test material
Molecular
Polymer/additive
(g/mol)
Polyethylene terephthalate
dimethyl terephthalate C10H10O4 194
methyl vinyl terephthalate C11H10O4 206
ethylene glycol C2H6O2 62
benzoic acid C7H6O2 122
vinyl benzoate C9H8O2 148
acetophenone C8H8O 120
ethylene dibenzoate C16H14O4 270
propionaldehyde C3H6O 58
benzene C6H6 78
acetaldehyde C2H4O 44
terephthalic acid C8H6O4 166
phthalic acid C8H6O4 166
isophthalic acid C8H6O5 166
acetic acid C2H4O3 60
glycerol C3H8O3 92
diethylene glycol C4H10O3 106
butyl benzoate C11H14O2 178
benzaldehyde C7H6O 106
2,4-dimethylpropylbenzoate C12H16O2 192
diethyl terephthalate C12H14O4 222
methylethyl terephthalate C11H12O4 208
cyclic trimer - 1576
(cyclic) oligomers - -
2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1-
phenylethyl)phenol C30H29N3O 448
benzotriazole C6H5N3 119
- 116 -
additives used in the manufacture of the PET test material
Molecular
Polymer/additive
(g/mol)
Hexanedioic acid polymer with 1,3-

benzenedimethanamine - -
hexanedioic acid C6H10O4 146
1,3-benzenedimethanamine C8H12N2 136
cyclopentanone C5H8O 84
2-cyclopentylcyclopentanone C10H16O 152
aminotoluene C7H9N 107
Copper phthalocyanine blue C32H16CuN8 576

phthalodinitrile C8H4N2 128
benzonitrile C7H5N 103
hydrogen cyanide HCN 27
- 117 -
used in the manufacture of the PVC test material
Molecular
Polymer/additive
(g/mol)
PVC
vinyl chloride C2H3Cl 62
benzene C6H6 78
aromatic hydrocarbons - -
PVC oligomers - -
Di-n-octyltin-bis(ethylmaleate) C28H48O8Sn 631

octane C8H18 114
maleic acid ethyl ester C6H8O4 144
maleic acid C4H4O4 116
n-octyltin-tris(ethylmaleate) C26H38O12Sn 661
di-n-octyltin-(ethylmaleate) chloride C22H41O4SnCl 523
n-octyltin-bis(ethylmaleate) chloride C20H31O8SnCl 553
Di-n-octyltin-bis(ethylhexylthioglycolate) C36H72O4S2Sn 751

2-ethylhexyl mercaptoacetate C10H20O2S 204
mercaptoacetic acid C2H4O2S 92
2-ethylhexanol C8H18O 130
n-octyltin-tris(ethylhexylthioglycolate) C38H74O6S3Sn 841
di-n-octyltin-(ethylhexylthioglycolate) chloride C26H53O2SSn 548
C28H55O4S2Sn
n-octyltin-bis(ethylhexylthioglycolate) chloride Cl 678
ESBO
linolenic acid C18H30O2
hydrochlorinated derivatives - -
allylic chlorinated ethers - -
cyclic degradation products - -
- 118 -
additives used in the manufacture of the PVC test material
Molecular
Polymer/additive
(g/mol)
Stearic acid C18H36O2 284

palmitic acid C16H32O2 256
ATBC C20H34O8 402

acetic acid C2H4O2 60
butanol C4H10O 74
acetyl dibutyl citrate C16H26O8 346
acetyl butyl citrate C12H18O8 290
butyl citrate C8H10O8 234
citric acid C6H8O7 192
Paraffin wax
alkanes
- 119 -
used in the manufacture of the PA test material
Polymer/additive Molecular
Proposed impurities/reaction/breakdown Molecular formula weight
products (g/mol)
Nylon
caprolactam C6H11NO 113
cyclopentanone C5H10O 86
2-methyl-pyridine C6H7N 93
pentanoic acid C5H10O2 102
butanamide C4H9NO 87
2-ethyl-cyclopentanone C7H14O 114
2,4,6-trimethyl-pyridine C8H11N 121
pentanamide C5H11NO 101
3-(1-methylethyl)-pyridine C8H11N 121
2-butyl-pyridine C9H13N 135
N,N-hexamethylenebisformamide C13H27NO 213
2-butyl-cyclopentanone C9H16O 140
glutarimide C5H7NO2 113
1-propyl-2,5-pyrrolidine-dione C7H11NO2 141
2-pentyl-cyclopentanone C10H18O 154
azepane-2,7-dione C6H9NO2 127
2-cyclopentyl-cyclo-pentanone C10H16O 152
1-butyl-2,5-pyrrolidine-dione C8H13NO2 155
1-pentyl-2,5-pyrrolidine-dione C9H15NO2 169
2-butyl-3,5-pyrrolidine-dione C8H13NO2 155
stearic acid C18H36O2 284
palmitic acid C16H32O2 256
Talc Mg3SiO12H2 294
Zinc stearate Zn(C18H35O2)2 632

stearic acid C18H36O2 284
- 120 -
Table 16. Molecular Feature Editor (MFE) parameters used in the LC-TOF-MS data
analysis
Number of C atoms: 0 - 100

Number of H atoms: 0 - 200
Number of O atoms: 0 - 20
Number of N atoms: 0 - 20
Number of P atoms: 0 - 10
Number of S atoms: 0-5
Number of Cl atoms: 0-5
Number of 2H atoms: 0 - 10
Number of Na atoms: 0-5
Number of Ca atoms: 0-5
Number of Cu atoms: 0-5
Number of Ti atoms: 0-5
Number of Si atoms: 0-5
Signal/noise threshold: 50
Minimum relative volume: 5%
Mass accuracy tolerance: 10 ppm
- 121 -
Table 17. Solutions of additives in ethanol and isooctane analysed by GC-MS
Detected in Detected in
Additive ethanol isooctane
extract extract
PP
Diparamethyldibenzylidene sorbitol No No
Tris(2,4-di-tert-butylphenyl)phosphate Yes Yes
No No
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-
2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-
No No
hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]],
Mn ca. 2000
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine
No No
ethanol-alt-1,4-butanedioic acid), Mn ca. 3500
Erucamide Yes Yes
Glycerol monostearate Yes No
Calcium carbonate No No
HDPE
* *
diylphosphonite
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate Yes Yes
Oleamide Yes Yes
Titanium dioxide No No
N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine # #
Glycerol monooleate Yes Yes
Sodium (C10-C18) alkyl sulfonate No No
2,5-Bis(5'-tert.butylbenzoxazol-2-yl)thiophene Yes Yes
PS
Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-
Yes Yes
m-tolyl)-propionate)
TNPP No No
DEHP Yes Yes
Bis(stearoyl)ethylenediamide No No
Polyethylene glycol 4-tert-octyl-phenyl ether, n~5 Yes Yes
Polyethylene glycol 4-tert-octyl-phenyl ether, n=9-10 No No
- 122 -
Table 17 continued. Solutions of additives in ethanol and isooctane analysed by GC-
MS
Additive Detected in Detected in

ethanol isooctane
extract extract
2-(2'-Hydroxy-5'-methylphenyl)benzotriazole Yes Yes
PET
Yes Yes
phenylethyl)phenol
No No
benzenedimethanamine
Copper phthalocyanine blue No No
PVC
Dioctyltin bis(ethylmaleate) No No
Dioctyltin bis(2-ethylhexyl thioglycolate)) No No
ESBO No No
Stearic acid No No
Acetyl tributyl citrate Yes Yes
Paraffin wax Yes Yes
PA
Talc No No
Zinc stearate No No
* Several peaks were detected in the chromatograms but none could be assigned to
tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite consistent with
reports of this additives instability in solution
# Several peaks were detected. The mass spectra derived were not consistent with
those expected for the standards
- 123 -
Table 18. Substances detected in the GC-MS TIC chromatograms of the solvent extracts of the PP + additives samples that were not present
in the extracts of the PP samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
Peak concentration concentration Proposed identity Present in/derived from Predicted
(minutes) (minutes)
(µg/dm2) (µg/dm2)
Ethanol Isooctane Ethanol Isooctane
Reaction/breakdown product
PP1 7.0-10.0 1168 glycerol derived from glycerol Yes
monostearate
PP2 8.5 8 butanedioic acid, dimethyl ester Reaction/breakdown product No
PP3 9.6 6.6 13 25 2-methylbenzaldehyde Reaction/breakdown product No
PP4 10.2 7.3 10 35 unknown Reaction/breakdown product No
derived from poly(4-hydroxy-
1-aza-2,2,6,6-tetramethyl-3-
PP5 13.9 6 2,2,6,6-tetramethyl-1- Yes
cyclohexeneethanol
piperidine ethanol-alt-1,4-
butanedioic acid),
PP6 15.4 16 unknown Reaction/breakdown product No
Present in tris(2,4-di-tert-
PP7 15.9 85 2,4-di-t-butyl phenol butylphenyl)phosphite Yes
standard
Present in glycerol
PP9 19.0 10 tetradecanoic acid, ethyl ester No
monostearate
- 124 -
Table 18 continued. Substances detected in the GC-MS TIC chromatograms of the solvent extracts of the PP + additives samples that were
not present in the extracts of the PP samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
Present in pentaerythritol
methyl-3-(3,5-di-tert-butyl-4- tetrakis(3,5-di-tert-butyl-4-
PP11 20.6 18.5 88 370 Yes
hydroxyphenyl)propionate hydroxyhydrocinnamate)
standard
Reaction/breakdown product,
PP12 20.8 21 hexadecanoic acid ions suggest derived from Yes
glycerol monostearate
Present in pentaerythritol
ethyl-3-(3,5-di-tert-butyl-4- tetrakis(3,5-di-tert-butyl-4-
PP13 21.2 178 Yes
hydroxyphenyl)propionate hydroxyhydrocinnamate)
standard
PP14 22.8 20.7 33 35 octadecanoic acid ions suggest derived from Yes
Present in glycerol
PP15 23.1 20.9 200 58 octadecanoic acid, ethyl ester- Yes
monostearate standard
ions suggest derived from
poly(4-hydroxy-2,2,6,6-
PP16 23.2 21.3 4 35 unknown No
tetramethyl-1-piperidine
ethanol-alt-1,4-butanedioic
acid),
- 125 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PP21 24.1 65 glycerol monotetradecanoate ions suggest derived from No
Present in erucamide
PP23 24.6 18 oleamide No
standard
Present in glycerol
PP24 24.6 28 eicosanoic acid, ethyl ester No
Present in glycerol
PP26 25.6 23.5 333 1578 unknown No
PP27 25.8 4698 glycerol monohexadecanoate ions suggest derived from No
- 126 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PP28 26.2 20 amide No
standard
Present in glycerol
PP31 27.0 18 unknown No
Present in glycerol
PP32 27.2 24.9 503 1258 unknown No
PP33 27.4 9670 glycerol monostearate Glycerol monostearate Additive
PP34 27.6 25.6 4 33 erucamide Erucamide Additive
PP35 27.9 35 alkyl amide No
standard
methyl-1-aza-2,2,6,6-tetramethyl-3- poly(4-hydroxy-2,2,6,6-
PP37 28.1 26.0 48 130 Yes
cyclohexeneethyl succinate tetramethyl-1-piperidine
acid),
- 127 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PP38 28.8 35 glycerol monoeicosanoate ions suggest derived from No
PP40 29.0 50 tetracosenamide No
standard
PP41 29.2 33 unknown No
standard
poly(4-hydroxy-2,2,6,6-tetramethyl-1-
poly(4-hydroxy-2,2,6,6-
PP43 29.9 27.9 18 25 piperidine ethanol-alt-1,4-butanedioic No
tetramethyl-1-piperidine
acid), monomer + piperidinyl ring
acid),
- 128 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
pentaerythritol tetrakis(3,5-di-tert- ions suggest derived from
PP46 28.9 25 butyl-4-hydroxyhydrocinnamate) pentaerythritol tetrakis(3,5-di- No
related tert-butyl-4-
PP47 29.3 33 unknown butylphenyl)phosphite No
standard
Tris(2,4-di-tert-
PP48 31.5 29.5 35 55 tris(2,4-di-tert-butylphenyl)phosphite Additive
butylphenyl)phosphite
oxidised tris(2,4-di-tert-
PP49 32.9 560 butylphenyl)phosphite Yes
standard
Present in poly[[6-[(1,1,3,3-
poly[[6-[(1,1,3,3- tetramethylbutyl)amino]-1,3,5-
tetramethylbutyl)amino]-1,3,5- triazine-2,4-diyl]-[(2,2,6,6-
triazine-2,4-diyl]-[(2,2,6,6- tetramethyl-4-
PP50 34.2 32.0 17885 1463 No
tetramethyl-4-piperidinyl)imino]-1,6- piperidinyl)imino]-1,6-
hexanediyl-[(2,2,6,6-tetramethyl-4- hexanediyl-[(2,2,6,6-
piperidinyl)imino]], repeating unit tetramethyl-4-
piperidinyl)imino]],
- 129 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PP53 36.6 105 (degradation product of) diglyceride ions suggest derived from No
pentaerythritol tetrakis(3,5-di-tert- ions suggest derived from
PP54 39.1 8 butyl-4-hydroxyhydrocinnamate) pentaerythritol tetrakis(3,5-di- No
related (3 subunits) tert-butyl-4-
PP55 39.7 178 (degradation product of) diglyceride ions suggest derived from No
- 130 -
Table 19. Substances detected in the GC-MS TIC chromatograms of the ethanol extracts of the HDPE + additives samples that were not
present in the ethanol extracts of the HDPE samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
alkane Reaction/breakdown product Yes
HDPE1 6.0 1 and and and
unknown Reaction/breakdown product No
HDPE2 6.6 3 nonanal Reaction/breakdown product No
HDPE3 9.2 1 2-methyl-dodecene Reaction/breakdown product Yes
derived from tetrakis(2,4-di-
HDPE4 9.3 4 p-t-butylphenol Yes
tert-butylphenyl)[1,1-biphenyl]-
4,4’-diylphosphonite
HDPE5 9.4 4 tridecane Reaction/breakdown product Yes
tetradecene Reaction/breakdown product Yes
HDPE7 11.3 16 unknown Reaction/breakdown product No
HDPE8 11.1 11.3 4 16 unknown Reaction/breakdown product No
HDPE9 11.1 11.4 6 24 unknown Reaction/breakdown product No
HDPE10 11.5 33 2-methoxy-1-octene Reaction/breakdown product No
HDPE11 11.4 11.7 8 37 2-tridecanone Reaction/breakdown product Yes
- 131 -
Table 19 continued. Substances detected in the GC-MS TIC chromatograms of the ethanol extracts of the HDPE + additives samples that were
not present in the ethanol extracts of the HDPE samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
Present in sodium (C10-C18)
HDPE12 11.8 12.1 60 138 pentadecane Yes
alkyl sulfonate standard
Present in tetrakis(2,4-di-tert-
HDPE13 12.1 12.2 12 458 2,4-bis(1,1-dimethylethyl)phenol butylphenyl)[1,1-biphenyl]- Yes
4,4’-diylphosphonite standard
HDPE14 12.2 43 tridecanal Reaction/breakdown product No
HDPE18 13.9 14.1 4 17 dodecanone Reaction/breakdown product Yes
Present in sodium (C10-C18)
HDPE19 14.2 14.4 72 182 heptadecane Yes
alkyl sulfonate standard
HDPE20 14.6 14 tridecyloxirane Reaction/breakdown product No
Present in N,N-bis-(2-
HDPE22 15.8 1 unknown hydroxyethyl)alkyl(C13- No
C15)amine standard
- 132 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
HDPE23 15.9 6 pentadecanoic acid, ethyl ester ions suggest related to No
glycerol monooleate
C15)amine standard
pentadecanitrile hydroxyethyl)alkyl(C13- No
HDPE25 16.3 16.5 4 11 C15)amine standard
and and and
Present in octadecyl 3,5-di-t-
methyl-3-(3,5-di-tert-butyl-4- butyl-4-
HDPE26 16.8 21 No
hydroxyphenyl)propionate hydroxyhydrocinnamate
standard
C15)amine standard
Present in glycerol
HDPE28 17.9 16 heptadecanoic acid, ethyl ester No
monooleate standard
- 133 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
HDPE29 17.9 28 octadecenoic acid, methyl ester ions suggest derived from No
glycerol monooleate
unknown hydroxyethyl)alkyl(C13- No
HDPE30 18.0 12 C15)amine standard
and and
and
Reaction/breakdown product No
unknown
pentadecanamide Present in oleamide No
HDPE32 18.1 44 hexadecanedioic acid Reaction/breakdown product No
C15)amine standard
- 134 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
unknown hydroxyethyl)alkyl(C13- No
HDPE34 18.1 18.3 7 41 C15)amine standard
and and
and
Present in oleamide standard No
unknown
HDPE36 18.4 23 1-hexadecanol Reaction/breakdown product No
C15)amine standard
HDPE38 18.6 18.8 17 95 unknown hydroxyethyl)alkyl(C13- No
C15)amine standard
HDPE40 19.1 9 octadecenoic acid ions suggest derived from Yes
oleamide
- 135 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
methyl oleate ions suggest derived from Yes
HDPE41 18.9 19.2 461 721 glycerol monooleate
and and and
hexadecenamide Present in oleamide standard No
HDPE42 19.0 19.3 48 23 hexadecanamide Present in oleamide standard No
HDPE43 19.4 405 docosane Reaction/breakdown product Yes
HDPE44 19.3 4 1-docosene Reaction/breakdown product Yes
HDPE46 19.4 19.7 13 32 unknown hydroxyethyl)alkyl(C13- No
C15)amine standard
HDPE47 19.8 82 unknown ions suggest derived from No
glycerol monooleate
- 136 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
C15)amine standard
HDPE53 20.6 429 oleamide Oleamide standard Additive
HDPE54 20.6 21.0 432 1267 oleamide Oleamide standard Additive
HDPE55 21.1 581 tetracosane Reaction/breakdown product Yes
HDPE56 21.4 1020 glycerol monooleate Glycerol monooleate standard Additive
Present in glycerol
HDPE63 23.0 15 unknown No
monooleate standard
- 137 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
HDPE64 23.5 387 unknown ions suggest derived from No
glycerol monooleate
HDPE65 24.6 2 cholesta-2,4-diene ions suggest derived from No
glycerol monooleate
Present in glycerol
HDPE66 24.6 24.9 19 11 cholesta-3,5-diene No
monooleate standard
HDPE67 26.0 2 unknown butylphenyl)[1,1-biphenyl]- No
- 138 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
Octadecyl 3,5-di-t-butyl-4-
octadecyl 3,5-di-t-butyl-4-
HDPE74 29.4 29.8 331 666 hydroxyhydrocinnamate Additive
hydroxyhydrocinnamate
standard
- 139 -
Table 20. Substances detected in the GC-MS TIC chromatograms of the solvent extracts of the PS + additives samples that were not present
in the extracts of the PS samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PS1 8.6 3 2-ethyl-1-hexanol Present in DEHP standard Yes
PS2 13.3 1 phthalic anhydride (or related) Reaction/breakdown product No
PS3 15.7 13.6 1 5 branched alkane Reaction/breakdown product No
PS4 15.9 3 benzothiophene related Reaction/breakdown product No
PS5 18.0 16.0 5 3 unknown Present in TNPP standard No
PS13 19.1 1 unknown Present in TNPP standard No
Present in
3-methyl-5-tert-butyl-4- ethylenebis(oxyethylene)bis-
PS14 19.6 17.6 2 1 Yes
hydroxyphenyl methylpropanoate (3-(5-tert-butyl-4-hydroxy-m-
tolyl)-propionate) standard
- 140 -
Table 20 continued. Substances detected in the GC-MS TIC chromatograms of the solvent extracts of the PS + additives samples that were
not present in the extracts of the PS samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
Present in
3-methyl-5-tert-butyl-4-hydroxyphenyl ethylenebis(oxyethylene)bis-
PS15 20.3 1 Yes
ethylpropanoate (3-(5-tert-butyl-4-hydroxy-m-
tolyl)-propionate) standard
2-(2’-hydroxy-5’- 2-(2’-Hydroxy-5’-
PS16 21.9 19.9 1 2 Additive
methylphenyl)benzotriazole methylphenyl)benzotriazole
2-(2-4(1,1,3,3- Present in polyethylene glycol
PS17 20.6 4 tetramethylbutyl)phenoxy)ethoxy) 4-tert-octyl-phenyl ether, n=9- No
ethanol 10 standard
PS18 25.4 23.5 20 80 isomer of DEHP Present in DEHP standard No
PS19 25.7 23.7 5 22 DEHP DEHP Additive
ethylenebis(oxyethylene)bis-(3-(5- Ethylenebis(oxyethylene)bis-
PS20 39.9 38.0 1 3 tert-butyl-4-hydroxy-m-tolyl)- (3-(5-tert-butyl-4-hydroxy-m- Additive
propionate) tolyl)-propionate)
- 141 -
Table 21. Substances detected in the GC-MS TIC chromatograms of the solvent extracts of the PET + additives samples that were not present
in the extracts of the PET samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PET1 26.2 43 unknown derived from copper No
phthalocyanin blue
2-(2H-Benzotriazole-2-yl)-4,6-
2-(2H-benzotriazole-2-yl)-4,6-bis(1-
PET2 32.9 75 bis(1-methyl-1- Additive
methyl-1-phenylethyl)phenol
phenylethyl)phenol
- 142 -
Table 22. Substances detected in the GC-MS TIC chromatograms of the solvent extracts of the PVC + additives samples that were not present
in the extracts of the PVC samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC1 3.9 3886 acetic acid, mercapto-, ethyl ester Reaction/breakdown product No
PVC2 4.2 60 p-vinylphenyl isothiocyanate Reaction/breakdown product No
PVC3 4.3 3 acetic acid Reaction/breakdown product Yes
PVC4 4.5 7 2,2,3,3-tetramethylbutane Reaction/breakdown product No
PVC5 4.5 17 alkene Reaction/breakdown product No
PVC6 5.0 24 2-pentylfuran Reaction/breakdown product No
PVC7 5.1 24 octanal Reaction/breakdown product No
Present in dioctyltin bis(2-
PVC8 5.5 5.6 73351 9136 2-ethyl-1-hexanol ethylhexyl thioglycolate) No
standard
PVC9 6.2 156 di-2-ethylhexyl chloroformate Reaction/breakdown product No
Present in dioctyltin
PVC10 6.5 8 unknown No
bis(ethylmaleate) standard
PVC11 6.5 10 alkane Reaction/breakdown product No
PVC12 6.6 16 nonanal Reaction/breakdown product No
PVC13 6.6 74 unknown Reaction/breakdown product No
PVC14 7.0 5 1-octanethiol Reaction/breakdown product No
- 143 -
Table 22 continued. Substances detected in the GC-MS TIC of the solvent extracts of the PVC + additives samples that were not present in the
extracts of the PVC samples (where no data is given the peak was not detected in that extraction solvent)
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC15 7.0 7.2 191 666 2-ethylhexyl acetate ethylhexyl thioglycolate) No
standard
PVC17 7.4 7.6 13 2345 2-butenedioic acid (Z)-, diethyl ester No
PVC18 7.5 7.7 108 6 carbonic acid dibutyl ester Reaction/breakdown product No
PVC19 7.6 7.8 49 56 2-butenedioic acid (E)-, diethyl ester No
PVC20 7.9 3 3-dodecene (E) Reaction/breakdown product No
PVC22 7.7 116 octanoic acid, ethyl ester Reaction/breakdown product No
PVC23 8.0 12 dodecane Reaction/breakdown product No
PVC24 8.1 3 decanal Reaction/breakdown product No
- 144 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC29 8.8 7 pentanoic acid,4-oxo-,butyl ester Reaction/breakdown product No
butanedioic acid, hydroxy-, diethyl
PVC30 8.9 8 Reaction/breakdown product No
ester
PVC31 9.0 1 1,1'-oxybishexane Reaction/breakdown product No
PVC35 9.4 9 tridecane Reaction/breakdown product No
PVC36 9.2 9.5 210 6 unknown Reaction/breakdown product No
PVC39 9.5 9.8 89 28 ethyl 3,3-diethoxypropionate No
PVC41 10.1 8 2-butenedioic acid (Z)-, diethyl ester Reaction/breakdown product No
- 145 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC42 10.2 69 chloroacetic acid, 2-ethylhexyl ester Reaction/breakdown product No
PVC46 10.7 10 1-tetradecene Reaction/breakdown product No
PVC50 11.0 70 2,6-(1,1-dimethylethyl)phenol Reaction/breakdown product No
PVC51 11.2 5891 isooctyl mercaptoacetate ethylhexyl thioglycolate) Yes
standard
PVC52 11.9 12.2 20380 6026 butylated hydroxytoluene No
PVC53 12.1 141 8-hexyl pentadecane No
- 146 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
bis(ethylmaleate) and
PVC55 12.3 12.6 142 302 7-methyl pentadecane No
dioctyltin bis(2-ethylhexyl
thioglycolate) standards
PVC56 12.5 12.8 192 317 7-methyl-octandecan-7-ol ethylhexyl thioglycolate) No
standard
PVC57 13.1 57 hexadecene Reaction/breakdown product No
PVC58 12.7 13.2 69 441 diethyl toluamide Reaction/breakdown product No
PVC59 12.8 345 2-butenedioic acid (Z)-, diethyl ester Reaction/breakdown product No
PVC60 12.9 10971 dibutyl itaconate Reaction/breakdown product No
PVC62 13.3 4450 hexadecane No
- 147 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC67 13.7 65 ethyl citrate Reaction/breakdown product No
PVC68 13.7 14.0 5255 9248 1,1'-oxybisoctane No
PVC73 14.6 33 p-toluenesulfonic acid, n-hexyl ester Reaction/breakdown product No
PVC75 14.8 20 o-acetylcitric acid triethyl ester Reaction/breakdown product No
benzenesulfonic acid, 4-methyl-, butyl
PVC76 14.6 14.9 1042 1033 Reaction/breakdown product No
ester
- 148 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
benzenesulfonic acid, 4-methyl-,
butylester
PVC83 16.5 56 nonadecane Reaction/breakdown product No
PVC84 16.3 8518 o-acetylcitric acid, triethyl ester Present in ATBC standard No
unknown Present in ESBO standard
PVC86 17.2 204156 and and No
unknown Present in ATBC standard
PVC87 17.4 196 hexadecanoic acid, ethyl ester Reaction/breakdown product No
PVC88 18.1 18.3 134061 706 unknown Present in ATBC standard No
1-propene-1,2,3-tricarboxylic acid,
PVC89 19.0 Present in ATBC standard No
tributyl ester
PVC90 19.2-19.8 19.9 269205 ATBC ATBC Additive
- 149 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC93 20.3 243 butyl citrate Present in ATBC standard Yes
PVC94 20.4 347 unknown Present in ATBC standard No
PVC96 20.5 861 unknown Present in ESBO standard No
PVC98 20.8 1419 octadecanoic acid, butyl ester Reaction/breakdown product No
PVC105 21.4 158 butyl citrate Present in ATBC standard No
- 150 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC109 21.4 538 tetracosane Reaction/breakdown product No
PVC116 22.2 237 di-2-ethylhexyl phthalate Reaction/breakdown product No
PVC117 23.0 673 unknown ethylhexyl thioglycolate) No
standard
hexadecanoic acid,2,3-
bis(acetyloxy)propyl ester
- 151 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
PVC121 23.4 389 diisononyl phthalate Reaction/breakdown product No
- 152 -
Average Average
tr tr
(minutes) (minutes)
(µg/dm2) (µg/dm2)
Many other peaks were detected originating from the paraffin wax, they are not detailed here, all gave best library matches of alkanes.
- 153 -
Table 23. Additional peaks observed in the concentrated ethanol extracts of PP + additives with GCxGC-TOF-MS
tr (minutes) tr (minutes)
Peak Proposed identity Derived from Predicted
1st dimension 2nd dimension
X1 14.1 1.19 unknown Reaction/breakdown product No
X3 16.1 1.48 2,6-dimethyl-2,5-heptadieen-4-one Reaction/breakdown product No
Derived from poly[[6-[(1,1,3,3-
tetramethylbutyl)amino]-1,3,5-
triazine-2,4-diyl]-[(2,2,6,6-
X4 16.3 1.40 2,2,6,6-tetramethyl-4-piperidinamine Yes
tetramethyl-4-piperidinyl)imino]-
1,6-hexanediyl-[(2,2,6,6-
X5 16.5 1.52 3,5,5-trimethyl-cyclohexen-1-one Reaction/breakdown product No
X6 16.7 1.35 unknown No
X7 17.1 1.47 2,2,6,6-tetramethyl-4-piperidinol Yes
X9 21.9 1.67 4-propylacetophenone Reaction/breakdown product No
- 154 -
Table 23 continued. Additional peaks observed in the concentrated ethanol extracts of PP + additives with GCxGC-TOF-MS
Derived from pentaerythritol
X11 29.1 1.82 quinine methide related tetrakis(3,5-di-tert-butyl-4- No
X13 29.9 1.73 3,5-di-tert-butyl-4-hydroxybenzaldehyde tetrakis(3,5-di-tert-butyl-4- Yes
X14 30.7 1.74 3,5-di-tert-butyl-4-hydroxyacetophenone tetrakis(3,5-di-tert-butyl-4- Yes
Derived from glycerol
X15 32.5 1.33 hexadecanoic acid, methyl ester No
monostearate
X16 35.6 1.36 octadecanoic acid, methyl ester No
monostearate
X17 36.5 2.75 4,4’-(1-methylethylidene)bisphenol Reaction/breakdown product No
X18 36.6 1.42 eicosanoic acid, methyl ester No
monostearate
- 155 -
Table 23 continued. Additional peaks observed in the concentrated ethanol extracts of PP + additives with GCxGC-TOF-MS
X19 38.0 1.97 3,5-di-tert-butyl-4-hydroxyphenyl + unknown tetrakis(3,5-di-tert-butyl-4- No
- 156 -
Table 24. Overview of additives analysed by LC-MS
Ethanol Isooctane#
tr APCI APCI APCI APCI
Component
(min) neg pos neg pos
Diparamethyldibenzylidene sorbitol 13.2 445.2 387.2 419.3
Tris(2,4-di-tert-butylphenyl)phosphite 29.8 647.5 647.5
24.4 1175.8 1194.8 1173.6 1194.8
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-
1,3,5-triazine-2,4-diyl]-[(2,2,6,6-
tetramethyl-4-piperidinyl)imino]-1,6- *
hexanediyl-[(2,2,6,6-tetramethyl-4-
piperidinyl)imino]],
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-
piperidine ethanol-alt-1,4-butanedioic *
acid),
Erucamide 21.6 338.4
Glycerol monostearate *
Calcium carbonate *
Ethylenebis(oxyethylene)bis-(3-(5-tert-
17.6 585.4 604.4 585.3 604.4
butyl-4-hydroxy-m-tolyl)-propionate)
TNPP 32.7 689.5 689.5
DEHP 22.0 391.3 391.3
Bis(stearoyl)ethylenediamide 28.7 593.6
400.4 400.3
Polyethylene glycol 4-tert-octyl-phenyl + x44 + x44
16.2
ether, n=9-10 (max. (max.
620) 620)
356.22 356.2
Polyethylene glycol 4-tert-octyl-phenyl +x44 + x44
16.2
ether, n~5 (max. (max.
488) 488)
2-(2'-Hydroxy-5'-
16.2 224.1
methylphenyl)benzotriazole
2-(2H-Benzotriazole-2-yl)-4,6-bis(1-
21.5 446.3 448.4 446.2 448.2
*
Copper phthalocyanine blue *
* Not detected
#
Note: the retention times for the additives in isooctane were somewhat different
compared to ethanol due to slight adjustment of the mobile phase gradient
- 157 -
Table 25. Additional peaks observed for PP + additives with LC-MS
Retention time Estimated concentration

(minutes) m/z (-) m/z (+) Proposed identity (mg/dm2)
EtOH/isooctane EtOH/isooctane
445.2 387.2
13.2 diparamethyldibenzylidene sorbitol 7.5
(M-CH3COOH)- (M+H)+
13.6 255.2 unknown
14.9 283.3 unknown
15.0 430.2 unknown
15.5 341.3 unknown
15.9/6.7 599.4 unknown
16.5 768.5 unknown
17.6/8.3 291.2 unknown
18.3 305.2 unknown
18.4 713.4 unknown
18.6 341.2 unknown
18.7/9.3 882.6 unknown
19.0 255.2 unknown
19.1 1051.7 unknown
19.4 655.4 unknown
20.3 283.3 341.3 unknown
20.6 1165.8 unknown
- 158 -
Table 25 continued. Additional peaks observed for PP + additives with LC-MS

22.1 987.6 unknown
22.2/12.4 934.7 unknown
22.3/12.5 915.6 unknown
23.0 971.6 unknown
23.2 1119.7 1138.8 unknown
23.6 468.4 unknown
23.8 915.6 unknown
pentaerythritol tetrakis(3,5-di-tert-butyl-4-
24.4/14.3 1175.8 (M-H)- 1194.8 (M+NH4)+ 5/125
27.4/17.3 473.3 (M-DTBP)- 663.5 (M+H)+ oxidised tris(2,4-di-tert-butylphenyl)phosphite
28.7/18.4 579.5 unknown
- +
29.7/19.5 457.3 (M-DTBP) 647.5 (M+H) tris(2,4-di-tert-butylphenyl)phosphite 42/112
30.5 607.6 unknown
DTBP = ditertbutylphenyl
- 159 -
Table 26. Additional peaks observed for PS + additives with LC-MS

polyethylene glycol 4-tert-octyl-phenyl ether,
16.3/7.0 356.3 + x44 n~5/polyethylene glycol 4-tert-octyl-phenyl ether, 0.50
n=9-10
ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-
17.9/8.6 585.3 (M-H)- 604.4 (M+NH4)+ 0.28/3.3
hydroxy-m-tolyl)-propionate)
22.0/12.5 391.3 (M+H)+ DEHP 3.5/35
26.8 565.6 unknown
29.6/19.4 705.5 (M+H)+ oxidised TNPP 0.013/1.5
-/22.2 689.5 (M+H)+ TNPP
Table 27. Additional peaks observed for PET + additives with LC-MS

17.1 768.2 unknown
2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-
21.5 446.2 448.2 0.13
phenylethyl)phenol
27.8 610.2 unknown
- 160 -
Table 28. Identities of the additional peaks observed for PP + additives with LC-FT-MS
Retention time
Mass accuracy
(minutes) m/z (-) m/z (+) Elemental composition* Proposed identity Predicted
(ppm)
EtOH/isooctane
13.2 445.1894 387.1799 C22H26O6 2.0 diparamethyldibenzylidene sorbitol Additive
13.6 255.2330 C16H32O2 0.5 hexadecanoic acid Yes
14.9 283.2638 C18H36O2 0.6 hectadecanoic acid Yes
C29H35O1P1 1.8
15.0 430.2433 C21H36O8N1 1.8 unknown No
C20H30O3N8 1.8
15.5 341.2699 C20H38O4 0.1 unknown No
C31H55O9N2 2.0
15.9/6.7 599.3900 unknown No
C39H54O2N1P1 2.0
16.5 768.5358 C49H73O3N2P1 2.0 unknown No
methyl-3-(3,5-di-tert-butyl-4-
17.6/8.3 291.1961 C18H28O3 0.1 Yes
hydroxyphenyl)propionate
ethyl-3-(3,5-di-tert-butyl-4-
18.3 305.2119 C19H30O3 1.3 Yes
hydroxyphenyl)propionate
C35H56O7N9 1.1
18.4 713.4130 C37H58O8N6 2.9 unknown No
C38H54O4N10 4.8
18.6 341.1967 C18H30O6 0.8 unknown No
- 161 -
Table 28 continued. Identities of the additional peaks observed for PP + additives with LC-FT-MS
Retention time
Mass accuracy
(ppm)
EtOH/isooctane
C45H75O8N10 0.1
18.7/9.3 882.5685 C47H77O9N7 1.4 unknown No
C48H73O5N11 2.9
C16H32O2 (-) hexadecanoic acid Yes
19.0 255.2332 313.2733 1.0
C19H36O3 (+) glycerol monohexadecanoate – H2O No
C57H96O10N8 0.5
19.1 1051.7172 C55H94O9N11 0.8 unknown No
C58H92O6N12 1.8
19.4 655.4231 C39H60O8 0.1 unknown No
C18H36O2 (-) stearic acid Yes
20.3 283.2646 341.3047 1.0
C21H40O3 (+) glycerol monostearate – H2O No
C60H100O12N11 0.6
C73H102O10N2 1.0
20.6 1165.7496 C72H96O5N9 1.0 unknown No
C61H96O8N15 1.7
C62H102O13N8 1.7
pentaerythritol tetrakis(3,5-di-tert-butyl-4-
22.1 987.6181 C59H88O12 2.2 No
hydroxyhydrocinnamate)- DTBP
C64H87O3P1 0.8
22.2/12.4 934.6387 C55H82O5N8 1.1 unknown No
C56H88O10N1 1.5
- 162 -
Table 28 continued. Identities of the additional peaks observed for PP + additives with LC-FT-MS
Retention time
Mass accuracy
(ppm)
EtOH/isooctane
C60H85O5P1 1.1
22.3/12.5 915.6072 unknown No
C67H80O2 1.4
C63H89O6P1 3.5
23.0 971.6290 unknown No
C59H88O11 3.7
pentaerythritol tetrakis(3,5-di-tert-butyl-
23.2 1119.7186 1138.7584 C69H100O12 3.0 4-hydroxyhydrocinnamate)– C4H8 (tert- No
butyl)
23.6 468.4414 C29H58O3N1 0.7 unknown No
23.8 915.6002 C56H84O10 0.9 unknown No
pentaerythritol tetrakis(3,5-di-tert-butyl-
24.4/14.3 1175.7781 1194.8201 C73H108O12 1.5 Additive
4-hydroxyhydrocinnamate)
oxidised tris(2,4-di-tert-
27.4/17.3 473.2815 663.4524 C42H63O4P 1.0 Yes
C35H69O3N2 1.1
28.7/18.4 579.5339 unknown No
C38H67N4 4.0
29.7/19.5 457.2898 647.54592 C42H63O3P 1.0 tris(2,4-di-tert-butylphenyl)phosphite Additive
30.5 607.5649 C40H71N4 2.0 unknown No
* elemental composition after correction for positive/negative charge and adducts (if known), see corresponding Table in the LC-MS section
(Table 25)
- 163 -
Table 29. Identities of the additional peaks observed for PS + additives with LC-FT-MS
Retention time
Mass accuracy
(ppm)
EtOH/isooctane
16.3/7.0 356.3 + - - polyethylene glycol 4-tert-octyl-phenyl
x44 ether, n~5/polyethylene glycol 4-tert- Additive
octyl-phenyl ether, n=9-10
17.9/8.6 585.3412 604.3824 C34H50O8 1.5 ethylenebis(oxyethylene)bis-(3-(5-tert-
Additive
butyl-4-hydroxy-m-tolyl)-propionate)
22.0/12.5 391.2839 C24H38O4 1.8 DEHP Additive
26.8 565.5660 C36H72O2N2 2.0 N,N-bis(stearoyl)ethylenediamide related
No
substance
29.6/19.4 705.4997 C45H69O4P 2.0 tris(nonylphenyl) phosphate Yes
-/22.2 689.5049 C45H69O3P 2.0 TNPP Additive
(Table 26)
- 164 -
Table 30. Identities of the additional peaks observed for PET + additives with LC-FT-MS
Retention time
Mass accuracy
(ppm)
EtOH/isooctane
17.1 768.1655 C38H30O15N3 1.7 unknown No
C36H29O14N6 1.7
21.5 446.2229 448.2382 C30H29N3O 1.0 2-(2H-benzotriazole-2-yl)-4,6-bis(1- Additive
27.8 610.2021 - unknown No
(Table 27)
- 165 -
Table 31. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with +ve ESI
Retention time
Additive Mass Elemental composition Mass error (ppm)
(minutes)
HDPE
Tetrakis(2,4-di-tert-butylphenyl)[1,1- Greater than 5 matches with
8.7 – 10.5 338.0957 NA
biphenyl]-4,4’-diylphosphonite mass error < 5 ppm
18.1 246.0810 NA
46.9 – 47.8 498.2083 NA
60.1 406.2057 NA
62.3 536.1410 NA
64.4 610.1604 NA
66.0 684.1795 NA
Oleamide 29.8 199.1936 C12H25NO -0.074
Oleamide 33.4 – 34.8 225.2093 C14H27NO 0.16
Oleamide 42.7 227.2249 C14H29NO -0.065
Oleamide 46.5 277.2406 C18H31NO 0.13
Oleamide 50.2 – 53.0 253.2406 C16H31N 0.13
Oleamide 53.0 – 57.2 279.2562 C18H33NO -0.053
- 166 -
Table 31 continued. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with +ve ESI
Retention time
(minutes)
HDPE
Oleamide 57.6 255.2562 C16H33NO -0.058
C18H35NO
Oleamide 59.1 – 59.7 281.2719 0.12
(oleamide)
Oleamide 61.8 283.2875 C18H37NO -0.053
TiO2 No peaks detected
C17H37NO2
N,N-Bis-(2-hydroxyethyl)alkyl(C13-
13.2 - 19.0 287.2719 (N,N-Bis-(2-hydroxyethyl)alkyl(C13- 1.8
C15)amine
C15)amine C13)
C19H41NO2
19.7 - 25.0 315.3137 (N,N-Bis-(2-hydroxyethyl)alkyl(C13- 1.6
C15)amine
C15)amine C15)
C21H45NO2
31.3 343.3450 (N,N-Bis-(2-hydroxyethyl)alkyl(C13- -0.088
C15)amine
C15)amine C17)
C21H40O4
Glycerol monooleate 59.8, 60.4, 60.8 356.2927 0.11
(glycerol monooleate)
Sodium (C10-C18) alkyl sulfonate 35.6 300.2301 C17H32O4 0.13
Sodium (C10-C18) alkyl sulfonate 51.6 302.2457 C17H34O4 -0.033
- 167 -
Retention time
(minutes)
HDPE
2,5-Bis(5'-tert.butylbenzoxazol-2-
No peaks detected
yl)thiophene
PVC
Dioctyltin bis(ethylmaleate) 7.3 – 7.9 172.0736 C8H12O4 0.23
Dioctyltin bis(ethylmaleate) 13.0 – 13.3 218.1154 C10H18O5 -0.10
Greater than 5 matches with
Dioctyltin bis(2-ethylhexyl thioglycolate) 16.0 238.0346 NA
mass error < 5 ppm
Dioctyltin bis(2-ethylhexyl thioglycolate) 19.2 360.2148 C18H32O7 -0.010
Dioctyltin bis(2-ethylhexyl thioglycolate) 31.0 314.0855 NA
mass error < 5 ppm
ESBO 62.0 364.2250 C21H32O5 0.070
ESBO 64.8 406.2203 C19H34O9 0.041
Stearic acid No peaks detected
C20H34O8
Acetyltributyl citrate 56.3 402.2254 0.078
(Acetyltributyl citrate)
Paraffin wax No peaks detected
- 168 -
Retention time
(minutes)
PA
Talc No peaks detected
Zinc stearate No peaks detected
- 169 -
Table 32. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with -ve ESI
Retention time
(minutes)
HDPE
42.5 252.1725 NA
Octadecyl 3,5-di-t-butyl-4-
No peaks detected
hydroxyhydrocinnamate
Eucamide 55.7 – 59.2 476.1687 NA
mass error < 5 ppm
TiO2 No peaks detected
N,N-Bis-(2-hydroxyethyl)alkyl(C13- Greater than 5 matches with mass
24.4 423.3196 NA
C15)amine error < 5 ppm
26.9 349.2828 C18H39NO5 -0.068
C15)amine
29.9 312.1759 NA
32.0 451.3509 NA
C22H42O6
Glycerol monooleate 60.0, 60.5, 61.0 402.2981 -0.098
(glycerol monooleate + CH2O2)
Sodium (C10-C18) alkyl sulfonate 23.7 – 26.0 278.1882 C17H26O3 0.018
Sodium (C10-C18) alkyl sulfonate 26.7 – 29.4 292.2068 C21H26N (unsaturated amine) 0.94
Sodium (C10-C18) alkyl sulfonate 30.0 – 33.3 306.2225 C22H28N (unsaturated amine) 1.0
- 170 -
Table 32 continued. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with -ve ESI
Retention time
(minutes)
HDPE
C23H30N
Sodium (C10-C18) alkyl sulfonate 34.1 – 39.2 320.2378 -0.078
(unsaturated amine)
2,5-Bis(5'-tert.butylbenzoxazol-2-
No peaks detected
yl)thiophene
PVC
Dioctyltin bis(ethylmaleate) No peaks detected
Dioctyltin bis(2-ethylhexyl thioglycolate) No peaks detected
ESBO No peaks detected
C18H36O2
Stearic acid 66.0 284.2715 -0.10
(stearic acid)
Acetyltributyl citrate No peaks detected
Paraffin wax No peaks detected
PA
Talc No peaks detected
Zinc stearate No peaks detected
- 171 -
Table 33. Positive ESI analysis of the ethanol extracts of the HDPE (final solvent acetonitrile) – substances that were only detected in the
HDPE + additives extracts
Retention Estimated Mass

time Mass concentration Elemental composition accuracy Proposed identity Predicted
(minutes) (µg/dm2) (ppm)
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
14.3 – 21.2 243.2562 17.9 C15H33NO -0.061 Yes
secondary amine C13
14.4 – 16.4 287.2824 1000 C17H37NO2 1.8 Additive
C13
Not N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
14.6 – 30.1 331.3086 C19H41NO3 -0.13 No
measurable* C13 (-2H) + CH2CH2OH
19.7 – 22.5 285.2668 12.6 C17H35NO2 0.071 No
C13 (-2H)
Not
20.0 – 21.7 303.2926 C21H39N -0.0016 unsaturated amine No
measurable*
Not
21.0 269.2719 C17H35NO 0.12 C15 unsaturated mono alcohol derivative No
measurable*
21.5 – 29.9 271.2875 88.4 C17H37NO -0.055 Yes
secondary amine C15
21.9 – 29.5 315.3137 947 C19H41NO2 1.6 Additive
C15
22.5 – 29.9 359.3399 C21H45NO3 1.4 No
measurable* C15 (-2H) + CH2CH2OH
30.8 313.2981 C19H39NO2 0.064 No
measurable* C15 - 2H
- 172 -
Table 33 continued. Positive ESI analysis of the ethanol extracts of the HDPE (final solvent acetonitrile) – substances that were only detected

31.2 – 34.7 343.3450 1260 C21H45NO2 -0.088 No
C17 (present in standard)
35.7 369.3243 C22H43NO3 0.014 No
measurable* unsaturated C16 derivative
42.8 227.2249 674 C14H29NO -0.065 unknown (present in oleamide standard) No
unsaturated amine (present in oleamide
50.0, 53.0 253.2406 589 C16H31N 0.13 No
standard)
Not C17 aliphatic chain di-acid (present in sodium
54.2, 56.5 328.2614 C19H36O4 0.12 No
measurable* (C10-C18) alkyl sulfonate standard)
55.6 – 57.2 279.2562 589 C18H33NO -0.053 unknown (present in oleamide standard) No
Not C14 unsaturated mono alcohol derivative
57.6 255.2562 C16H33NO -0.058 No
measurable* (present in oleamidestandard)
59.0 – 59.6 281.2719 863 C18H35NO 0.12 oleamide Additive
59.9, 60.5,
356.2927 2630 C21H40O4 0.11 glycerol monooleate Additive
60.9
* Not measurable as no peak was observed in the TIC and therefore the peak area could not be compared with the internal standard
- 173 -
Table 34. Positive ESI analysis of the isooctane extracts of the HDPE (final solvent acetonitrile) – substances that were only detected in the

27.6 – 30.2 287.2824 103 C17H37NO2 1.8 Additive
C13
27.8 – 31.3 331.3086 C19H41NO3 1.5 No
measurable* C13 + CH2CH2OH
34.0 – 38.3 315.3137 71.6 C19H41NO2 1.6 Additive
C15
Not C21H45NO3 (C15H30N(CH2CH2OH)2 +
34.5 – 39.6 359.3399 C21H45NO3 1.4 No
measurable* CH2CH2OH)
Not
56.9 338.2457 C20H34O4 1.6 unknown No
measurable*
Not
57.7, 58.0 278.1518 C16H22O4 1.9 dibutyl phthalate (isomers) No
measurable*
62.8, 63.1 281.2719 147 C18H35NO 0.12 oleamide Additive
63.6, 63.9 356.2927 358 C21H40O4 0.11 glycerol monooleate Additive
- 174 -
Table 35. Negative ESI analysis of the ethanol extracts of the HDPE (final solvent acetonitrile) – substances that were only detected in the

Not
23.9 – 27.3 278.1882 C17H26O3 0.018 unknown No
measurable*
Not
27.6 – 30.0 292.2068 C21H26N 0.94 unsaturated amine No
measurable*
Not
30.5 – 34.4 306.2225 C22H28N 1.0 unsaturated amine No
measurable*
Not
34.9 – 40.0 320.2378 C23H30N -0.078 unsaturated amine No
measurable*
60.0, 60.6, Not
402.2981 C22H42O6 -0.098 glycerol monooleate + CH2O2 No
61.1 measurable*
- 175 -
Table 36. Positive ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in the PVC +
additives extracts

Not
3.3 – 4.5 190.0841 C8H14O5 0.23 unknown No
measurable*
Not unknown (present in dioctyltin bis(ethylmaleate)
5.6 172.0736 C8H12O4 -0.12 No
measurable* standard)
Not
8.4 264.0676 C8H12O4 -0.12 unknown No
measurable*
Not
12.4 276.1222 C12H20O7 4.6 unknown No
measurable*
Not unknown (present in dioctyltin bis(ethylmaleate)
12.9 – 14.4 218.1154 C10H18O5 2.4 No
measurable* standard)
Not Greater than 5 matches
15.3 432.2547 NA unknown No
measurable* with mass error < 5 ppm
Not
15.8 191.1310 C12H17NO -0.074 unknown No
measurable*
Not Greater than 5 matches unknown (present in dioctyltin bis(2-ethylhexyl
16.7 – 17.2 238.0346 NA No
measurable* with mass error < 5 ppm thioglycolate) standard)
Not
18.8 304.1529 C14H24O7 2.2 unknown No
measurable*
Not
19.9 318.1318 C14H22O8 1.0 unknown No
measurable*
- 176 -
Table 36 continued. Positive ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in

Not
21.4 304.1529 C14H24O7 2.2 unknown No
measurable*
23.1, 24.3, Not Greater than 5 matches
346.1634 NA unknown No
28.9 measurable* with mass error < 5 ppm
Not
25.8, 26.4 386.2671 C21H38O6 0.67 unknown No
measurable*
Not
27.9 390.2984 C21H42O6 0.66 unknown No
measurable*
Not
31.4 354.2415 C20H34O5 2.4 unknown No
measurable*
Not
32.2, 33.2 416.2087 C20H32O9 2.6 unknown No
measurable*
Not
38.0 374.1961 C20H29O8 0.11 unknown No
measurable*
- 177 -
Table 36 continued. Positive ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in

Not unknown (present in dioctyltin bis(2-ethylhexyl
40.0 360.1248 C18H32O7 -0.010 No
measurable* thioglycolate) standard)
- 178 -
Table 37. Positive ESI analysis of the isooctane extracts of the PVC (final solvent acetonitrile) – substances that were only detected in the PVC
+ additives extracts

Not
3.0 190.0841 C8H14O5 -0.12 unknown No
measurable*
Not
7.6 366.1923 C18H22O8 -6.6 unknown No
measurable*
Not
10.6 – 26.6 402.2261 C20H34O8 1.8 unknown No
measurable*
Not
19.3 318.1318 C14H22O8 1.0 unknown No
measurable*
Not
20.5 – 23.0 246.1467 C12H22O5 -0.097 unknown No
measurable*
Not
25.6 346.1641 C16H26O8 3.8 unknown No
measurable*
29.9 – 30.7 418.2216 NA unknown No
Not
32.2 – 38.5 416.2087 C20H32O9 4.1 unknown No
measurable*
Not
39.5 374.1961 C20H29O8 -2.1 unknown No
measurable*
- 179 -
Table 37 continued. Positive ESI analysis of the isooctane extracts of the PVC (final solvent acetonitrile) – substances that were only detected
in the PVC + additives extracts

Not unknown (present in dioctyltin bis(2-ethylhexyl
41.0 360.2148 C18H32O7 -0.010 No
measurable* thioglycolate) standard)
- 180 -
Table 38. Negative ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in the PVC
+ additives extracts

Not
1.9 264.0661 C8H22O4 1.3 unknown No
measurable*
Not
4.5 214.1205 C11H18O4 -0.043 unknown No
measurable*
Not
8.4 228.1362 C12H20O4 0.17 unknown No
measurable*
Not
12.9 242.1518 C13H22O4 -0.038 unknown No
measurable*
Not
16.0 – 16.4 450.2829 C22H42O9 0.036 unknown No
measurable*
19.5 – 20.8 456.2762 NA unknown No
Not
24.0 422.2880 C21H42O8 -1.2 unknown No
measurable*
Not
25.7 – 26.5 432.2571 C31H32N2 1.2 unknown No
measurable*
Not
28.0 436.3045 C22H44O8 2.0 unknown No
measurable*
Not
30.2 442.2931 C24H42O7 0.10 unknown No
measurable*
- 181 -
Table 38 continued. Negative ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in

Not
36.0 404.2774 C21H40O7 -0.010 unknown No
measurable*
Not
40.1 – 41.8 418.2957 C25H40NO4 -0.081 unknown No
measurable*
Not
43.5 782.5234 C54H69O4 -3.4 unknown No
measurable*
Not
54.4 376.2852 C21H44O2 4.8 unknown No
measurable*
Not
56.7 586.3532 C34H50O8 4.4 unknown No
measurable*
Not
64.0 730.5355 C54H68N 0.44 unsaturated amine No
measurable*
- 182 -
Table 39. Negative ESI analysis of the isooctane extracts of the PVC (final solvent acetonitrile) – substances that were only detected in the
PVC + additives extracts

Not
9.3 228.1362 C12H20O4 0.17 unknown No
measurable*
Not
13.7 242.1518 C13H22O4 -0.038 unknown No
measurable*
Not
44.9 432.2571 C31H32N2 1.2 unknown No
measurable*
Not
56.8 586.3532 C34H50O8 4.4 unknown No
measurable*
61.7 541.9472 NA unknown – Contains Cl atoms No
* Not measurable as no peak was observed in the TIC chromatograms and therefore the peak area could not be compared with the internal
standard
- 183 -
Table 40. Migration modelling data
Concentration in the polymer (µg/dm2) giving rise to 10 µg/kg migration

PP HDPE PS PET
100 Da substance 4 2 125 129
500 Da substance 33 17 1144 1148
1000 Da substance 189 95 6600 6720
- 184 -
Figure 1. Thermodesorption GC-MS chromatograms of PP and PP + additives
Abundance
TIC: FSA003.D
6000000
5000000
PP
4000000
3000000
2000000
1000000
0
6.00 8.0010.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.0032.00
Time-->
Abundance
TIC: FSA005.D
6000000
5000000
PP + additives
4000000
3000000
2000000
1000000
0
6.00 8.0010.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.0032.00
Time-->
- 185 -
Figure 2. Thermodesorption GC-MS chromatograms of HDPE and HDPE + additives
Abundance
TIC: rxn_230107_008.D
5.5e+07
HDPE
5e+07
4.5e+07
4e+07
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
5.00 10.00 15.00 20.00 25.00 30.00

Time-->
Abundance
TIC: rxn_230107_010.D
5.4e+07
5.2e+07
5e+07
4.8e+07
HDPE + additives
4.6e+07
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
5.00 10.00 15.00 20.00 25.00 30.00

Time-->
- 186 -
Figure 3. Thermodesorption GC-MS chromatograms of PS and PS + additives
Abundance
TIC: FSA011.D
4000000
PS
3500000
3000000
2500000
2000000
1500000
1000000
500000
0
6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.0032.00
Time-->
Abundance
TIC: FSA013.D
4000000
3500000 PS + additives
3000000
2500000
2000000
1500000
1000000
500000
0
6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.0032.00
Time-->
- 187 -
Figure 4. Thermodesorption GC-MS chromatograms of PET and PET + additives
Abundance
TIC: FSA007.D
500000 PET
450000
400000
350000
300000
250000
200000
150000
100000
50000
0
6.00 8.0010.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.0032.00
Time-->
Abundance
TIC: FSA009.D
500000
450000
PET + additives
400000
350000
300000
250000
200000
150000
100000
50000
0
6.00 8.0010.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.0032.00
Time-->
- 188 -
Figure 5. Thermodesorption GC-MS chromatograms of PVC and PVC + additives
Abundance
TIC: rxn_230107_013.D
PVC
5e+07
4.8e+07
4.6e+07
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
5.00 10.00 15.00 20.00 25.00 30.00

Time-->
Abundance
TIC: rxn_230107_015.D
4.4e+07
4.2e+07
4e+07
PVC + additives
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
5.00 10.00 15.00 20.00 25.00 30.00

Time-->
- 189 -
Figure 6. Thermodesorption GC-MS chromatograms of PA and PA + additives
Abundance
TIC: rxn_230107_029.D
3.2e+07
3e+07
PA
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
5.00 10.00 15.00 20.00 25.00 30.00

Time-->
Abundance
TIC: rxn_230107_031.D
3e+07
2.8e+07
PA + additives
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
5.00 10.00 15.00 20.00 25.00 30.00

Time-->
- 190 -
Figure 7. Best library match of the peak eluting at retention time 11.5 minutes in the
thermodesorption GC-MS chromatogram of the HDPE + additives sample
Abundance
Average of 11.490 to 11.519 min.: rxn_230107_010.D (-)

43
9000
8000
7000
6000
5000
4000
3000
2000
74
1000 281
94112133 169188207 239258 311 342361 399 429
0
50 100 150 200 250 300 350 400 450
m/z-->
Abundance
#799: 2-Propanone, 1-hydroxy-

43
9000
8000
7000
6000
5000
4000
3000
2000
74
1000 15
0
50 100 150 200 250 300 350 400 450
m/z-->
- 191 -
thermodesorption GC-MS chromatogram of the HDPE + additives sample
Abundance

45
9000
8000
7000
6000
5000
4000
3000
2000
1000
76 104 133 165 189207 237255 281299 325344364383402 429
0
0 50 100 150 200 250 300 350 400
m/z-->
Abundance
#918: Propylene Glycol

45
9000
8000
7000
6000
5000
4000
3000
2000
1000 27
76
0
0 50 100 150 200 250 300 350 400
m/z-->
- 192 -
thermodesorption GC-MS chromatogram of the PVC + additives sample
Abundance

31
9000
8000
7000
6000
5000
4000
3000
2000
1000
51 73 96 133 165183 207227250 286 311 343362385 415433
0
0 50 100 150 200 250 300 350 400
m/z-->
Abundance
#92: Ethanol
31
9000
8000
7000
6000
5000
4000
3000
2000
1000
12
0
0 50 100 150 200 250 300 350 400
m/z-->
- 193 -
Abundance

56
9000
8000
7000
6000
31
5000
4000
3000
2000
1000
74 92 119 151 181 207225 252 281301323341359377397 430
0
20 40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
Abundance
#822: 1-Butanol
56
9000
8000
7000
31
6000
5000
4000
3000
2000
1000
74
0
20 40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 194 -
Abundance

57
9000
8000
7000
6000
5000
4000
3000
83
2000
1000 31
112
141 166 197 232252 276296315 343362384403 432
0
50 100 150 200 250 300 350 400 450
m/z-->
Abundance
#13220: 1-Hexanol, 2-ethyl-

57
9000
8000
7000
6000
5000
4000
3000
2000 29 83
1000
112
0
50 100 150 200 250 300 350 400 450
m/z-->
- 195 -
Figure 12. GC-MS chromatograms of ethanol extracts of PP and PP + additives full
scale and zoomed in to show low intensity peaks
Abundance
TIC: FSA_013.D
4e+07 PP
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_015.D
4e+07 PP + additives
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_013.D
1600000 PP
1400000
1200000
1000000
800000
600000
400000
200000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_015.D
1600000 PP + additives
1400000
1200000
1000000
800000
600000
400000
200000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
- 196 -
Figure 13. GC-MS chromatograms of isooctane extracts of PP and PP + additives full
Abundance
TIC: FSA_089.D
3e+07 PP
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
TIC: FSA_091.D
PP + additives
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
PP TIC: FSA_089.D
1500000
1000000
500000
0
10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00
Time-->
Abundance
PP + additives TIC: FSA_091.D
1500000
1000000
500000
0
10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00
Time-->
- 197 -
Figure 14. GC-MS chromatograms of the concentrated ethanol extracts of PP and PP
+ additives full scale and zoomed in to show low intensity peaks
Abundance
TIC: FSA_198.D
1.8e+07
1.6e+07
PP
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_199.D
1.8e+07
1.6e+07
PP + additives
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_198.D
3500000
PP
3000000
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_199.D
3500000
PP + additives
3000000
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
- 198 -
Figure 15. GC-MS chromatograms of ethanol extracts of HDPE and HDPE + additives
full scale and zoomed in to show low intensity peaks
Abundance
TIC: RXN_LSCREEN_160207_020.D
3e+07
HDPE
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
3.5e+07 HDPE + additives

3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE
7000000
6000000
5000000
4000000
3000000
2000000
1000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE + additives
7000000
6000000
5000000
4000000
3000000
2000000
1000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 199 -
Figure 16. GC-MS chromatograms of isooctane extracts of HDPE and HDPE +
additives full scale and zoomed in to show low intensity peaks
Abundance
HDPE
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE + additives
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE TIC: RXN_LSCREEN_060207_014.D

8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE + additives
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 200 -
Figure 17. GC-MS chromatograms of concentrated ethanol extracts of HDPE and
HDPE + additives full scale and zoomed in to show low intensity peaks
Abundance
6e+07 HDPE
5.5e+07
5e+07
4.5e+07
4e+07
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
1.6e+08 HDPE + additives
1.4e+08
1.2e+08
1e+08
8e+07
6e+07
4e+07
2e+07
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE
7000000
6000000
5000000
4000000
3000000
2000000
1000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE + additives
7000000
6000000
5000000
4000000
3000000
2000000
1000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 201 -
Figure 18. GC-MS chromatograms of the concentrated isooctane extracts of HDPE
and HDPE + additives full scale and zoomed in to show low intensity peaks
Abundance

1.3e+08
1.2e+08
1.1e+08
1e+08
9e+07
8e+07
7e+07
6e+07
5e+07
4e+07
3e+07
2e+07
1e+07
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
HDPE + additives TIC: RXN_LSCREEN_060207_023.D
1.6e+08
1.4e+08
1.2e+08
1e+08
8e+07
6e+07
4e+07
2e+07
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
4.5e+07
4e+07
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
5e+07 HDPE + additives TIC: RXN_LSCREEN_060207_023.D
4.5e+07
4e+07
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 202 -
Figure 19. GC-MS chromatograms of ethanol extracts of PS and PS + additives full
Abundance
PS TIC: FSA_039.D
1e+07
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
PS + additives TIC: FSA_041.D

1e+07
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
PS TIC: FSA_039.D
400000
350000
300000
250000
200000
150000
100000
50000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
400000
350000
300000
250000
200000
150000
100000
50000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
- 203 -
Figure 20. GC-MS chromatograms of isooctane extracts of PS and PS + additives full
Abundance
PS TIC: FSA_109.D
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
TIC: FSA_109.D
3000000 PS
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
TIC: FSA_111.D
3000000 PS + additives
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
- 204 -
Figure 21. GC-MS chromatograms of the concentrated ethanol extracts PS and PS +
Abundance
TIC: FSA_202.D
PS
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_203.D
PS + additives
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_202.D
PS
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_203.D
PS + additives
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
- 205 -
Figure 22. GC-MS chromatograms of the concentrated isooctane extracts PS and PS
+ additives full scale and zoomed in to show low intensity peaks
Abundance
PS TIC: FSA_217.D
4.5e+07
4e+07
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
4.5e+07
4e+07
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
1e+07
PS TIC: FSA_217.D
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
TIC: FSA_218.D
1e+07 PS + additives
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
- 206 -
Figure 23. GC-MS chromatograms of ethanol extracts of PET and PET + additives
Abundance
TIC: FSA_028.D
200000 PET
180000
160000
140000
120000
100000
80000
60000
40000
20000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_030.D
200000
180000
PET + additives
160000
140000
120000
100000
80000
60000
40000
20000
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
- 207 -
Figure 24. GC-MS chromatograms of isooctane extracts of PET and PET + additives
Abundance
TIC: FSA_104.D
PET
1400000
1200000
1000000
800000
600000
400000
200000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
TIC: FSA_106.D
1400000 PET + additives

1200000
1000000
800000
600000
400000
200000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
- 208 -
Figure 25. GC-MS chromatograms of the concentrated ethanol extracts of PET and
PET + additives full scale and zoomed in to show low intensity peaks
Abundance
TIC: FSA_196.D
PET
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_197.D
PET + additives
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
Time-->
Abundance
TIC: FSA_196.D
PET
140000
120000
100000
80000
60000
40000
20000
0
22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00 38.00 40.00
Time-->
Abundance
PET + additives TIC: FSA_197.D
140000
120000
100000
80000
60000
40000
20000
0
22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00 38.00 40.00
Time-->
- 209 -
Figure 26. GC-MS chromatograms of the concentrated isooctane extracts of PET and
PET + additives full scale and zoomed in to show low intensity peaks
Abundance
TIC: FSA_213.D
3000000
PET
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
TIC: FSA_214.D
3000000
PET + additives
2500000
2000000
1500000
1000000
500000
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time-->
Abundance
TIC: FSA_213.D
500000
PET
450000
400000
350000
300000
250000
200000
150000
100000
50000
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

Time-->
Abundance
TIC: FSA_214.D
500000
PET + additives
450000
400000
350000
300000
250000
200000
150000
100000
50000
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

Time-->
- 210 -
Figure 27. GC-MS chromatograms of ethanol extracts of PVC and PVC + additives full
Abundance
2.4e+07
PVC
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
2e+08
PVC + additives
1.8e+08
1.6e+08
1.4e+08
1.2e+08
1e+08
8e+07
6e+07
4e+07
2e+07
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
PVC + additivesTIC: RXN_LSCREEN_160207_035.D

2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 211 -
Figure 28. GC-MS chromatograms of isooctane extracts of PVC and PVC + additives
full scale and zoomed in to show low intensity peaks
Abundance
2400000 PVC
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
1.8e+08
PVC + additives
1.6e+08
1.4e+08
1.2e+08
1e+08
8e+07
6e+07
4e+07
2e+07
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
2400000
PVC + additivesTIC: RXN_LSCREEN_060207_030.D
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 212 -
Figure 29. GC-MS chromatograms of ethanol extracts of PA and PA + additives full
Abundance
5500000
5000000
PA
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
5000000 PA + additives
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
800000
750000
700000
PA
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00
Time-->
Abundance
800000
750000
700000 PA + additives
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00
Time-->
- 213 -
Figure 30. GC-MS chromatograms of isooctane extracts of PA and PA + additives
Abundance
1000000 PA
900000
800000
700000
600000
500000
400000
300000
200000
100000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
900000
PA + additives
800000
700000
600000
500000
400000
300000
200000
100000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 214 -
Figure 31. GC-MS chromatograms of concentrated ethanol extracts of PA and PA +
Abundance
5e+07
4.5e+07
PA
4e+07
3.5e+07
3e+07
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
3e+07
PA + additives
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
5500000
5000000
PA
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
5500000
5000000
PA + additives
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 215 -
Figure 32. GC-MS chromatograms of concentrated isooctane extracts of PA and PA +
Abundance
4000000
PA
3500000
3000000
2500000
2000000
1500000
1000000
500000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
8000000
7000000
PA + additives
6000000
5000000
4000000
3000000
2000000
1000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
800000
750000 PA
700000
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
Abundance
800000
750000
700000
PA + additives
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 216 -
Figure 33. GCxGC-TOF-MS chromatograms of ethanol extracts of (A) PP and (B) PP
+ additives
- 217 -
Figure 34. GCxGC-TOF-MS chromatograms of isooctane extracts of (A) PP and (B)
PP + additives
- 218 -
Figure 35. GCxGC-TOF-MS chromatograms of concentrated ethanol extracts of (A)
PP and (B) PP + additives
- 219 -
Figure 36. GCxGC-TOF-MS chomatograms of ethanol extracts of (A) HDPE and (B)
HDPE + additives
- 220 -
Figure 37. GCxGC-TOF-MS chromatograms of isooctane extracts of (A) HDPE and
(B) HDPE + additives
- 221 -
HDPE and (B) HDPE + additives
- 222 -
Figure 39. GCxGC-TOF-MS chromatograms of concentrated isooctane extracts of (A)
HDPE and (B) HDPE + additives
- 223 -
Figure 40. GCxGC-TOF-MS chromatograms of ethanol extracts of (A) PS and (B) PS
+ additives
- 224 -
Figure 41. GCxGC-TOF-MS chromatograms of isooctane extracts of (A) PS and (B)
PS + additives
- 225 -
PS and (B) PS + additives
- 226 -
PS and (B) PS + additives
- 227 -
PET and (B) PET + additives
- 228 -
PET and (B) PET + additives
- 229 -
PA and (B) PA + additives
- 230 -
PA and (B) PA + additives
- 231 -
Figure 48. GCxGC-TOF-MS chromatogram of a concentrated ethanol extract of PP + additives with the additional peaks detected in the
second dimension highlighted
- 232 -
Figure 49. Base peak LC-MS chromatograms of ethanol extracts of PP
C:\LCMS data\...\9feb07\EtOH_APCI_NEG-03 10/02/2007 09:58:53 0940/01/3561 A
RT: 0.00 - 35.01 SM: 3B

NL: 3.08E7
Base Peak m/z=
100
150.00-1250.00 F: FTMS
90 PP APCI- - c APCI corona Full ms [
150.00-1500.00] MS
80 EtOH_APCI_NEG-03
Relative Abundance
70
60
50
40
30
20
10
0
24.37 NL: 3.08E7
1175.77 Base Peak m/z=
100
150.00-1250.00 F: FTMS
90 PP + additives APCI- - c APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_neg-06
Relative Abundance
70
60
50
40
30
13.19
20 445.19
17.61 22.29 27.42 29.67
10 291.20 915.60 473.28 457.29
0
0 5 10 15 20 25 30 35
Time (min)
C:\LCMS data\...\9feb07\EtOH_APCI_POS_03 09/02/2007 18:31:13 0940/01/3561 A
RT: 0.00 - 35.01 SM: 3B

NL: 1.10E8
Base Peak m/z=
100
150.00-1200.00 F: FTMS
90 PP APCI+ + c APCI corona Full ms [
150.00-1500.00] MS
80 EtOH_APCI_POS_03
Relative Abundance
70
60
50
40
30
20
10 27.44 29.81
680.48 647.46
0
24.40 NL: 1.10E8
1194.82 29.74 Base Peak m/z=
100 647.46 150.00-1200.00 F: FTMS
90 PP + additives APCI+ + c APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_pos_05
Relative Abundance
70
60
50
40
30
20 27.44
13.18 22.26 663.45 30.41
10 387.18 18.66 934.64 607.56
882.57
0
0 5 10 15 20 25 30 35
Time (min)
- 233 -
Figure 50. Base peak LC-MS chromatograms of isooctane extracts of PP
c:\lcms data\...\isooct_apci_neg_04 14/02/2007 09:44:49 0940/01/3561 B
RT: 0.00 - 35.00 SM: 3B

NL: 5.09E6
Base Peak m/z=
100
PP APCI- 150.00-1250.00 F: FTMS
- c APCI corona Full ms [
90
150.00-1500.00] MS
80 isooct_apci_neg_04
Relative Abundance
70
60
50
40
30
20
14.44 17.18
10 1175.77 473.28
0
14.32 NL: 5.09E6
100
150.00-1250.00 F: FTMS
90
PP + additives APCI- - c APCI corona Full ms [
150.00-1500.00] MS
Relative Abundance
70
60
50
40
30 14.45
1175.78 19.42
20 12.47 457.29
8.27 915.60
10
291.20
0
0 5 10 15 20 25 30 35
Time (min)
C:\LCMS data\...\ISOOCT_APCI_POS_03 13/02/2007 17:41:54 0940/01/3561 A
RT: 0.00 - 35.01 SM: 3B

19.53 NL: 5.42E7
100
14.45
90
PP APCI+ 1194.82
150.00-1200.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
80 ISOOCT_APCI_POS_03
17.34
663.45
Relative Abundance
70
60
50
40
30
20
10 13.90
20.55
934.64
647.46
0
19.44 NL: 1.84E8
100
150.00-1200.00 F: FTMS
90 PP + additives APCI+ + c APCI corona Full ms [
150.00-1500.00] MS
80 isooct_apci_pos_05
Relative Abundance
70
14.35
60 1194.82
33.21
50
599.55
40
17.28
30 663.45
20.14
20 647.46
10 5.89 9.34 10.74 21.34 32.15
430.24 882.57 996.61 647.46 599.55
0
0 5 10 15 20 25 30 35
Time (min)
- 234 -
Figure 51. Base peak LC-MS chromatograms of ethanol extracts of PS
c:\lcms data\...\9feb07\etoh_apci_neg-24 10/02/2007 23:06:35 0940/01/3571 B
RT: 0.00 - 35.01 SM: 3B

26.68 NL: 2.57E6
100
150.00-1000.00 F: FTMS
90 PS APCI- - c APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_neg-24
Relative Abundance
70
60
50
40 18.59
341.20
30
23.15 23.82
20 15.02 341.20 341.20 27.53
283.26 29.85
341.20
3.27 6.83 9.25 11.54 341.20
10
341.20 341.20 341.20 341.20
0
17.92 NL: 2.44E6
100
150.00-1000.00 F: FTMS
90 PS + additives APCI- - c APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_neg-26
Relative Abundance
70
60
50
40
30
20 26.70
20.91 22.06 529.46
10 1.69 3.47 6.67 9.37 15.03 341.20 341.20 27.40
341.20 341.20 341.20 341.20 283.26 358.42
0
0 5 10 15 20 25 30 35
Time (min)
etoh_apci_pos_24_070215005635 15/02/2007 00:56:35 0940/01/3571 B
RT: 0.00 - 45.00 SM: 3B

NL: 5.84E6
Base Peak m/z=
100
90
PS APCI+ 150.00-1000.00 F: FTMS + c
APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_pos_24_0702150
05635
Relative Abundance
70
60
50
40
0.60
30
420.26
20 2.27
420.26 3.91 44.71
10 21.98 32.24 33.28 420.26
420.26 403.23 403.23
395.31
0
21.97 NL: 5.84E6
100
150.00-1000.00 F: FTMS + c
90 PS + additives APCI+ APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_pos_26
Relative Abundance
70
60
50 17.93
604.38
40
30 4.85
420.26 5.72 26.78
420.26 16.33 565.57
20 444.33 29.61
7.78 26.57 31.54 44.43
10 10.26 705.50 35.43
420.26 936.75 403.23 420.26
420.26 403.23
0
0 5 10 15 20 25 30 35 40
Time (min)
- 235 -
Figure 52. Base peak LC-MS chromatograms of isooctane extracts of PS
c:\lcms data\...\isooct_apci_neg_24 14/02/2007 21:38:17 0940/01/3571 B
RT: 0.00 - 34.99 SM: 3B

NL: 4.64E6
Base Peak m/z=
100
PS APCI- 150.00-1000.00 F: FTMS
90 - c APCI corona Full ms [
150.00-1500.00] MS
Relative Abundance
70
60
50
40
30
20
10
0
8.59 NL: 4.64E6
100
PS + additives APCI- 150.00-1000.00 F: FTMS
- c APCI corona Full ms [
90
150.00-1500.00] MS
Relative Abundance
70
60
50
40
30
20
9.21
10 341.20
0
0 5 10 15 20 25 30
Time (min)
c:\lcms data\...\isooct_apci_pos_25 14/02/2007 06:46:31 0940/01/3572 A
RT: 0.20 - 32.36 SM: 3B

NL: 2.21E7
Base Peak m/z=
100
PS APCI+ 150.00-1000.00 F: FTMS
90
150.00-1500.00] MS
Relative Abundance
70
60
50
40
30
20
9.21
10 420.26 15.57 19.54 22.19
403.23 647.46 403.23
0
12.40 NL: 2.21E7
100
150.00-1000.00 F: FTMS
90 PS + additives APCI+ + c APCI corona Full ms [
150.00-1500.00] MS
Relative Abundance
70
60
50
40
8.56
30 604.38
19.33
20 7.01 705.50
444.33 22.31
10 12.73 18.50 689.51 23.13
391.28 403.23 703.52
0
5 10 15 20 25 30
Time (min)
- 236 -
Figure 53. Base peak LC-MS chromatograms of ethanol extracts of PET
c:\lcms data\...\9feb07\etoh_apci_neg-16 10/02/2007 18:21:05 0940/01/3567 B
RT: 0.00 - 35.00 SM: 3B

NL: 1.13E6
Base Peak m/z=
100
150.00-1000.00 F: FTMS
90 PET APCI- - c APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_neg-16
Relative Abundance
70
16.06
60 576.13
50
40
30
20
15.65
11.01 622.17 17.07 23.98 25.22 29.17 30.74
10
251.13 768.17 358.42 923.55 358.42 923.57
0
21.50 NL: 1.13E6
100
150.00-1000.00 F: FTMS
90 PET + additives APCI- - c APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_neg-18
Relative Abundance
70 16.07
576.13
60
50
40
30
20 17.07
15.63 768.16
10 10.91 622.17 20.30 24.42 30.86 32.97
251.13 537.64 358.42 923.56 358.42
0
0 5 10 15 20 25 30 35
Time (min)
c:\lcms data\...\9feb07\etoh_apci_pos_16 10/02/2007 02:15:04 0940/01/3567 B
RT: 0.00 - 35.01 SM: 3B

33.02 NL: 2.33E5
100
150.00-1000.00 F: FTMS
90
PET APCI+ + c APCI corona Full ms [
150.00-1500.00] MS
80 etoh_apci_pos_16
Relative Abundance
70
60
50
40
30
21.98 28.67
20 27.80 607.57
395.31 607.57
10 4.04 16.05
395.31 577.13
0
21.49 NL: 2.22E5
100
150.00-1000.00 F: FTMS
90 PET + additives APCI+ 33.00
150.00-1500.00] MS
80 395.41 etoh_apci_pos_18
Relative Abundance
70
60
50
40
27.78
30 610.18
21.97
20 395.31 26.69
537.63 30.06
10 2.66 5.26 16.06 20.95 684.20
395.31 264.17 577.13 860.29
0
0 5 10 15 20 25 30 35
Time (min)
- 237 -
Figure 54. Base peak LC-MS chromatograms of isooctane extracts of PET
C:\LCMS data\...\ISOOCT_APCI_NEG_15 14/02/2007 16:17:10 0940/01/3567 A
RT: 0.00 - 35.01 SM: 3B

33.31 NL: 3.44E3
100
150.00-1000.00 F: FTMS
90 - c APCI corona Full ms [
150.00-1500.00] MS
80 PET APCI- ISOOCT_APCI_NEG_15
Relative Abundance
70
60
50 0.66
655.42
2.45
40
655.42 6.79 9.26 14.20 17.73 21.54 27.36 29.62
30 576.13 358.42 358.42 358.42 358.42 358.42 358.42
20
10
0
0.94 NL: 1.07E3
655.42 23.62 Base Peak m/z=
100 7.36 10.95 17.20 358.42 30.96 33.11
3.31 12.26 19.17 28.52 150.00-1000.00 F: FTMS
358.42 358.42 358.42 358.42 537.64 358.42 358.42 358.42
655.42 - c APCI corona Full ms [
90
150.00-1500.00] MS
Relative Abundance
70
60
PET + additives APCI-
50
40
30
20
10
0
0 5 10 15 20 25 30 35
Time (min)
c:\lcms data\...\isooct_apci_pos_18 14/02/2007 02:36:52 0940/01/3568 B
RT: 0.00 - 32.70 SM: 3B

19.52 NL: 2.71E5
100
150.00-1000.00 F: FTMS
90 + c APCI corona Full ms [
150.00-1500.00] MS
80 PET APCI+ isooct_apci_pos_16
Relative Abundance
70
17.28
60
663.45
50
40
30 20.51
13.45 16.20 403.23 22.13
0.13
20 2.28 403.23 403.23 403.23
420.26 9.23 24.15 26.08
420.26 31.16
403.23 403.23 403.23
10 403.23
0
19.52 NL: 3.60E5
100
150.00-1000.00 F: FTMS
90 + c APCI corona Full ms [
150.00-1500.00] MS
PET + additives APCI+
Relative Abundance
70
60
17.29
50 663.45
40
20.68
30 21.97
403.23
403.23
20 12.43 16.40
9.23 23.61
2.60 3.72 395.31 403.23 25.86 28.76
10 403.23 403.23
403.23 420.26 403.23 403.23
0
0 5 10 15 20 25 30
Time (min)
- 238 -
Figure 55. Total ion chromatogram for HDPE and HDPE + additives (isooctane
extraction, final solvent acetonitrile) in positive mode electrospray TOF-MS
- 239 -
Figure 56. Total ion chromatogram for HDPE and HDPE + additives (ethanol
extraction, final solvent acetonitrile) in positive mode electrospray TOF-MS
- 240 -
Figure 57. Total ion chromatogram for HDPE and HDPE + additives (isooctane
extraction, final solvent acetonitrile) in negative mode electrospray TOF-MS
- 241 -
Figure 58. Total ion chromatogram for HDPE and HDPE + additives (ethanol
extraction, final solvent acetonitrile) in negative mode electrospray TOF-MS
- 242 -
Figure 59. Total ion chromatogram for PVC and PVC + additives (isooctane extraction,
final solvent acetonitrile) in positive mode electrospray TOF-MS
- 243 -
Figure 60. Total ion chromatogram for PVC and PVC + additives (ethanol extraction,
- 244 -
Figure 61. Total ion chromatogram for PVC and PVC + additives (isooctane extraction,
final solvent acetonitrile) in negative mode electrospray TOF-MS
- 245 -
Figure 62. Total ion chromatogram for PVC and PVC + additives (ethanol extraction,
- 246 -
Figure 63. Total ion chromatogram for PA and PA + additives (isooctane extraction,
- 247 -
Figure 64. Total ion chromatogram for PA and PA + additives (ethanol extraction, final
solvent acetonitrile) in positive mode electrospray TOF-MS
- 248 -
Figure 65. Total ion chromatogram for PA and PA+ additives (isooctane extraction,
- 249 -
Figure 66. Total ion chromatogram for PA and PA + additives (ethanol extraction, final
solvent acetonitrile) in negative mode electrospray TOF-MS
- 250 -
Figure 67. Stacked 1H 1D NMR spectroscopy plot of a solvent blank, PP extract and
PP + additives extract
Solvent blank
PP blank
PP + additives
Figure 68. Stacked 1H 1D NMR spectroscopy plot of the additives used in the
preparation of the PP test materials compared to the PP extracts and PP + additives
extracts
PP additive 1
PP additive 2
PP additive 3
PP additive 4
PP additive 5
PP additive 6
PP blank
PP + additives
PP additive 1 = Pentaerythritol tetrakis(3,5,di-tert-butyl-4-hydroxyhydrocinnamate)

PP additive 2 = Glycerol monostearate
PP additive 3 = Diparamethyldibenzylidene sorbitol
PP additive 4 = Tris(2,4-di-tertbutylphenyl)phosphite
PP additive 5 = Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-
butanedioic acid
PP additive 6 = Erucamide
- 252 -
preparation of the PP test materials compared to the PP extracts and PP + additives
extracts. Highlighted regions contain resonances from breakdown products or other
impurities
PP additive 1 = Pentaerythritol tetrakis(3,5,di-tert-butyl-4-hydroxyhydrocinnamate)

PP additive 2 = Glycerol monostearate
PP additive 3 = Diparamethyldibenzylidene sorbitol
PP additive 4 = Tris(2,4-di-tertbutylphenyl)phosphite
PP additive 5 = Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-
butanedioic acid
PP additive 6 = Erucamide
- 253 -
Figure 70. Stacked 1H 1D NMR spectroscopy plot of a solvent blank, HDPE extract
and HDPE + additives extract
Solvent blank
HDPE blank
HDPE + additives
- 254 -
preparation of the HDPE test materials compared to the HDPE extracts and HDPE +
additives extracts
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate
Oleamide
Glycerol monooleate
2,5-Bis(5'-tert.butylbenzoxazol-2-yl)thiophene
HDPE blank
HDPE + additives
- 255 -
preparation of the HDPE test materials compared to the HDPE extracts and HDPE +
additives extracts. Highlighted regions contain resonances from breakdown products
or other impurities
HDPE additive 1 = Sodium (C10-C18) alkyl sulfonate

HDPE additive 2 = Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
HDPE additive 3 = Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate
HDPE additive 4 = N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine
HDPE additive 5 = Oleamide
HDPE additive 6 = Glycerol monooleate
HDPE additive 7 = 2,5-Bis(5'-tert.butylbenzoxazol-2-yl)thiophene
- 256 -
Figure 73. Stacked 1H 1D NMR spectroscopy plot of a solvent blank, PS extract and
PS + additives extract
Solvent blank
PS blank
PS + additives
- 257 -
preparation of the PS test materials compared to the PS extracts and PS + additives
extracts
PS additive 1
PS additive 2
PS additive 3
PS additive 4
PS additive 5
PS blank
PS + additives
PS additive 1 = Polyethylene glycol 4-tert-octyl-phenyl ether, n~5

PS additive 2 = Polyethylene glycol 4-tert-octyl-phenyl ether, n=9-10
PS additive 3 = DEHP
PS additive 4 = Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-
propionate)
PS additive 5 = 2-(2’-Hydroxy-5’-methylphenyl)benzotriazole
- 258 -
Figure 75. Stacked 1H 1D NMR spectroscopy plot of a solvent blank, PET extract and
PET + additives extract
Solvent blank
PET blank
PET + additives
- 259 -
preparation of the PET test materials compared to the PET extracts and PET +
additives extracts
phenylethyl)phenol
PET blank
PET + additives
- 260 -
preparation of the PET test materials compared to the PET extracts and PET +
additives extracts. Highlighted regions contain resonances from breakdown products
or other impurities
- 261 -
Figure 78. Stacked 1H 1D NMR spectroscopy plot of a solvent blank, PVC extract and PVC
+ additives extract
Solvent blank
PVC blank
PVC + additives
- 262 -
preparation of the PVC test materials compared to the PVC extracts and PVC +
additives extracts
ESBO
Dioctyltin bis(2-ethylhexyl thioglycolate)
Dioctyltin bis(ethylmaleate)
Tributyl acetylcitrate
Stearic acid
PVC blank
PVC +additives
- 263 -
Figure 80. Stacked 1H 1D NMR spectroscopy plot of the PVC + additives extract, the
PVC blank extract and the ATBC standard. The displayed resonances can not be
assigned to ATBC and are hypothesised to be impurities present in the standard.
These impurities are also present in the PVC + additives sample extract
ATBC
PVC blank
PVC + additives
- 264 -
Figure 81. Stacked 1H 1D NMR spectroscopy plot of a solvent blank, PA extract and
PA + additives extract
Solvent blank
PA blank
PA + additives
- 265 -
1
Figure 82. H–1H TOCSY NMR spectrum of the region 5.2 – 1.9 ppm of the CDCl3
extract of the PP + additives extract
- 266 -
Figure 83. 1H–1H overlaid TOCSY NMR spectra of the region 5.2 – 1.9 ppm of the PP
without additives extract, pentaerythritol tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate), glycerol monostearate, diparamethyldibenzylidene sorbitol
and poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid)
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid)

Diparamethyldibenzylidene sorbitol
Glycerol monostearate
Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)
PP without additives
- 267 -
1
Figure 84. H–1H TOCSY NMR spectrum of the region 5.2 – 1.9 ppm of the PP +
additives extract. Off-diagonal crosspeaks correlating the resonances 4.80, 4.52, 4.46
and 3.74 ppm are highlighted in green, off diagonal crosspeaks from a hypothesised
glycerol monostearate breakdown product are highlighted in yellow
- 268 -
13
Figure 85. C–1H HSQC NMR spectrum of the region 1H = 5.4 – 3.0 and 13C = 80 – 45
ppm of the PP + additives extract
- 269 -
13
Figure 86. C–1H overlaid HSQC NMR spectrum of the region 1H = 5.4 – 3.0 and 13
C
= 80 – 45 ppm of the PP without additives extract, pentaerythritol tetrakis(3,5-di-tert-
butyl-4-hydroxyhydrocinnamate), glycerol monostearate, diparamethyldibenzylidene
sorbitol and poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic
acid)
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid)

Diparamethyldibenzylidene sorbitol
Glycerol monostearate
Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)
PP without additives
- 270 -
13
Figure 87. C–1H HSQC NMR spectrum of the region 1H = 5.4 – 3.0 and 13C = 80 – 45
ppm of the PP + additives extract. Resonances that are not observed in the overlay
spectra shown in Figure 86 are highlighted in yellow
- 271 -
ANNEX 1
Mass spectra of each substance detected in the additives
- 272 -
PEAKS DETECTED IN THE CHROMATOGRAMS OF THE PP ADDITIVES
Mass spectra of peaks detected when the solvent standards of

diparamethylenedibenzylidene sorbitol were analysed by GC-MS
No peaks detected
Mass spectra of peaks detected when the solvent standards of tris(2,4-di-tert-

butylphenyl)phosphite were analysed by GC-MS
2,4-DI-T-BUTYL PHENOL – impurity in or breakdown product of tris(2,4-di-tert-

Abundance

11500 191
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
57
1500
1000
163
74 91 115
500
133 208 267
40 230249 291 325 355 387 415
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 273 -
UNKNOWN – impurity in or breakdown product of tris(2,4-di-tert-butylphenyl)phosphite
Abundance

17000 57
16000
281
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
197
2000 147 237
1000 91 175
117 219
255 329
311 357 385 416 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(2,4-di-tert-butylphenyl)phosphite

Abundance

21000 385
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000 57
8000
7000
6000
5000
147
4000 441
3000
2000
97
1000 119 313
78 175 210 237255 355
273293 331 404
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 274 -
TRIS(2,4-DI-TERT-BUTYLPHENYL)PHOSPHITE ISOMER
Abundance

60000 441
55000
50000
45000
40000
35000
30000
25000
20000
57
15000
10000
147 308
5000
91 191 235 385
117 173 253 284 329 413
210 359
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
TRIS(2,4-DI-TERT-BUTYLPHENYL)PHOSPHITE
Abundance

441
5000000
4500000
4000000
3500000
3000000
57
2500000
2000000
147
1500000
1000000
308
500000 191
91 237
119 219 385
329
173 255273291 347367 411
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 275 -
OXIDISED TRIS(2,4-DI-TERT-BUTYLPHENYL)PHOSPHITE ISOMER – impurity in or
breakdown product of tris(2,4-di-tert-butylphenyl)phosphite
Abundance

210000 316
200000
190000
180000
170000
160000
150000
57
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000 191
40000
147
30000
20000 91 291
253
117
10000 367 443
173
222 345 403423
271 385
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of pentaerythritol

tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) were analysed by GC-MS
METHYL-3-(3,5-DI-TERT-BUTYL-4-HYDROXYPHENYL)PROPIONATE – impurity in
or breakdown product of pentaerythritol tetrakis(3,5-di-tert-butyl-4-
Abundance

55000 277
50000
45000
40000
35000
30000
25000
20000
15000
147 219
10000 57
5000
91 128 185
109 167 249 295 327 355 387 415 442
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 276 -
ETHYL-3-(3,5-DI-TERT-BUTYL-4-HYDROXYPHENYL)PROPIONATE – impurity in or
breakdown product of pentaerythritol tetrakis(3,5-di-tert-butyl-4-
Abundance

11500 291
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
147
219
3500
3000
2500
57
2000
1500
1000 189
91 128
500 249
171 341 415
109 267 320 387 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 277 -
Mass spectra of peaks detected when the solvent standards of poly[[6-[(1,1,3,3-
tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-
piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] were
analysed by GC-MS
POLY[[6-[(1,1,3,3-TETRAMETHYLBUTYL)AMINO]-1,3,5-TRIAZINE-2,4-DIYL]-
[(2,2,6,6-TETRAMETHYL-4-PIPERIDINYL)IMINO]-1,6-HEXANEDIYL-[(2,2,6,6-
TETRAMETHYL-4-PIPERIDINYL)IMINO]] REPEATING UNIT – impurity in or
breakdown product of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-
piperidinyl)imino]]
Abundance

9500 98 124
9000
8500
8000
7500 58
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
237
2000
1500
1000 181 256
500 155
336 394 416
79 209 296 356
40 315 376 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 278 -
UNKNOWN – impurity in or breakdown product of poly[[6-[(1,1,3,3-
tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-
piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]
Abundance

55000 124
50000
45000
40000
58
35000 321
30000
25000
20000
15000 209
98
10000 348
167 235 388
5000 275 418 444
79 147 191 293
40 253 370
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of poly(4-hydroxy-

2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid) were analysed
by GC-MS
No peaks detected
- 279 -
Mass spectra of peaks detected when the solvent standards of erucamide were
analysed by GC-MS
9-OCTADECENAMIDE – impurity in or breakdown product of erucamide

Abundance

15000 59
14000
13000
12000
11000
10000
9000
8000
7000
6000 41
5000
4000
81
3000
126
2000
100
1000 154
178198 220238 264
282 326 356 401 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of erucamide

Abundance

32000 55
30000
28000
26000
24000
22000
20000 83
122
18000
16000
14000
12000
319
10000 276
150
8000
178 248
6000 206
4000
2000
224 341 401 429
103 295 359 383
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 280 -
ETHYL-13-DOCOSENOATE – impurity in or breakdown product of erucamide
Abundance

55
8500
8000
7500
7000
6500
6000
5500
5000
83
4500 320
4000
3500
3000
101
2500
2000
1500 123 236 278
1000 207
155 366
500 179 341 415
254 302 388
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
EICOSENAMIDE – impurity in or breakdown product of erucamide

Abundance

59
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000 41
14000
12000
10000
8000 83
126
6000 309
4000
154 207 266
2000 101 182 226 248 341
284 366 401 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 281 -
EICOSENAMIDE – impurity in or breakdown product of erucamide
Abundance

8500
59
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500 41
309
114 207 281
1000 86
500 154 235 341

134 178 262 387 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

55
6000
5500
5000
4500
4000
83
3500
122
193
3000
2500
2000
319
1500
276
150
248
1000 220
500
168
103
295 339358 417
385 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 282 -
ERUCAMIDE
Abundance

59
1800000
1600000
1400000
1200000
1000000
800000
600000 41
83 337
400000
126
200000
154 294
101 184 240 263
212 319 355 387 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
ERGOSTA-4,6,22-TRIENE – impurity in or breakdown product of erucamide

Abundance

380
5000
4500
4000
3500
3000
2500 81
207
255
2000
105
1500 55
145
1000
281
500 123 175 228 355
313 337 402
429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 283 -
Abundance

96
5000
55
4500
4000
3500
3000
2500
2000
1500 124
265
1000 418
399
500 152
191 220 292
245 327 371
77 345 445
173
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

6500 55
6000
5500
5000
82
4500
4000
3500
3000
2500
110 418
2000
1500
207
138
1000 341
268 306
500 180 396
161 235
286 369 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 284 -
Abundance

382
2800
2600
2400
2200
2000
1800
1600
1400
1200 147
1000 43
430
800 105
81
600 261
213
400
129
295
200 192
173
235 326 403
63 344
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
TETRACOSENAMIDE – impurity in or breakdown product of erucamide

Abundance

59
60000
55000
50000
45000
40000
35000
30000
25000
20000 41
15000 83
10000 365
114
5000 207
135154 281 322
184 240 263 304 385
341 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 285 -
Abundance

12000 382
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500 147
5000
4500
4000
3500 105
3000
2500
2000 274
213 255
1500
1000
129
58 79 173
500 191 356 401
320 429
238
298 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

396
5000
4500
4000
3500
3000
207
2500
2000
91
43
1500 147
255
1000
69
119 281
341
177 429
500
228 312
373
448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 286 -
Abundance

396
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
147
9000
8000
7000 43
6000
81 105
5000
4000 207
255
3000 275
2000 129
173
1000 228 355
296 327 415
61 373 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of glycerol

monostearate were analysed by GC-MS
HEXADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol

monostearate
Abundance

88
120000
110000
100000
90000
80000
70000
60000
50000
40000
43
30000
157 284
20000 70 241
10000 115 199 306

219
139 175 263 341 401
383 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 287 -
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance

117
4500
4000
3500
3000
2500
2000
75
1500
1000
45 191
500 96
137 223 265

283 325 415
165 241 356 385 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
OCTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol

monostearate
Abundance

88
220000
200000
180000
160000
140000
120000
100000
80000
43 312
60000
157
269
40000 69
20000 115 213
139 185 241

295 341 369387 415 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 288 -
Abundance

130
4000
3500
3000
2500
2000
1500
207
343
1000 57
101
500 281
177
325
75
157 403
229 251 431
299 369
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
EICOSANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol

monostearate
Abundance

6500 88
6000
5500
5000
4500
4000
3500
3000
43
340
2500
117
2000
1500 157
207 297
69
1000
500
255
135 185 359
227 401 429
279 315 383 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 289 -
Abundance

130000
130
120000
110000
100000
90000
80000
70000
60000
50000
40000
371
30000 43 239
101
20000
71
315
10000 190
259 343
149 171 208 281 401 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

75000 117
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
313
15000 43
207
10000 98
75 371
147 281
5000 239
259 341
171
189 389 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 290 -
Abundance

120000 130
110000
100000
90000
80000
70000
60000
50000
40000
399
30000
43
101 267
20000
71
203 343
10000
173 371
149 221 245 285 315 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

117
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000 341
18000
16000
14000
12000
10000
8000 207
6000
4000 73 98 147 281

414
2000 315
171 227 259 371
54 189 389 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 291 -
Abundance

415
26000
24000
22000
20000
18000 191
16000
14000
12000
10000 133
8000
221
6000
73 163
4000 281
43
2000 355
95
114 239 261 311 333 387 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of calcium

carbonate were analysed by GC-MS
No peaks detected
- 292 -
PEAKS DETECTED IN THE CHROMATOGRAMS OF THE HDPE ADDITIVES
Mass spectra of peaks detected when the solvent standards of tetrakis(2,4-di-

tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite were analysed by GC-MS
2,4-DI-T-BUTYL PHENOL – impurity in or breakdown product of tetrakis(2,4-di-tert-

butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
Abundance
Average of 11.488 to 11.522 min.: RXN_800_310307_005.D (-)

191
1600000
1500000
1400000
1300000
1200000
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
57
200000
100000 163
91 115
133
209 251 281 316 342 415 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1-

biphenyl]-4,4’-diylphosphonite
Abundance

1600 57
1500
1400
1300
1200
85
1100
1000
900
800
700
600
500 111 210
400
355
300
200 415
141
40 182 265 325
100 282
163
246
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 293 -
Abundance

57
2000
1800
1600
1400 85
1200
1000
800
111
600
210
400
200 265 341

141 387
179 430
40 161 283
369
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

57
900
800
85
700
600
500
111
400
300
192
211 282
200
163 429
100 135 251
357
401
40 309329
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 294 -
SUBSTITUTED BIPHENYL – impurity in or breakdown product of tetrakis(2,4-di-tert-
Abundance

246
2400
154
2200
2000 218
1800
1600
1400
1200
1000 55
800
600
83
400 127 199
177 267
200
327 415
102
297 356 387 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

55000 218
50000
45000
246
154
40000
35000
30000
25000
20000
15000
10000
5000 77 115 199

51 181
96 134 265283 312330 356 383401 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 295 -
Abundance

1600 57
1500
1400
1300
1200
1100 85
1000
900
800
700
600 224
111
500
400
300
200 174
282
207
100 249 356 415

148 325
130 378 432

0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

338
4500
152 282
4000
219
3500
3000
2500
2000
1500
247 310
1000
97
201
65 183
500 126
47 416
358 385 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 296 -
Abundance

282
32000
30000
28000
26000
24000 338
22000
152
20000
18000
16000 219
14000
12000
10000
8000
309
247
6000
201
4000
2000 65 183
47 126
102 389 429
83 357 411 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

595
200000
180000
160000
140000
120000
100000
290
80000
57
60000
349
40000
147 191
20000 539
91 389 441
252 483
637 699
730 772
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 297 -
Abundance

38000 347
36000
291
34000
32000
30000
28000
26000
24000
57
22000
20000
552
18000
16000
14000
12000
10000
8000
427
6000
191
91 147
4000 495
2000
235
396 461 595 638 697 754
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->

Abundance

385
60000
55000
50000
45000 441
40000
35000
30000
57
25000
20000
590
15000
91 147
10000 280
5000
191 237
329
475 519
551 624 679
711 757
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 298 -
Abundance

38000 385
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000 57
12000
10000 590
441
8000
147
6000 280
207
4000
91
2000 329
249 475
506 550 638 698 752
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
TRIS(2,4-DI-TERT-BUTYLPHENYL)PHOSPHITE – impurity in or breakdown product

of tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
Abundance

441
5000000
4500000
4000000
3500000
3000000
2500000
2000000
57
1500000
646
1000000 147
308
500000
191
91 237
385
273 345 477 533 589 698 738771
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 299 -
Abundance

160000 389
150000
140000
130000
120000
333
110000
100000
90000
80000
594
70000
60000 57
50000
40000
282
30000
20000 183
427 537
91 147
10000
219 495
461 639 697 738772
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z-->

Abundance

389
1200000
1100000
1000000
900000
800000
700000
600000
500000
333
400000
594
300000
57
200000
183
100000 427
147 282 537
91
235 462495 637 698 744 786
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 300 -
Mass spectra of peaks detected when the solvent standards of octadecyl 3,5-di-t-
butyl-4-hydroxyhydrocinnamate were analysed by GC-MS
METHYL-3-(3,5-DI-TERT-BUTYL-4-HYDROXYPHENYL)PROPIONATE – impurity in
or breakdown product of octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate
Abundance

42000 277
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
147
10000
219
8000
57
6000
4000
91 185
2000
327356 401 475 550 711

0
50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
ETHYL-3-(3,5-DI-TERT-BUTYL-4-HYDROXYPHENYL)PROPIONATE – impurity in or
breakdown product of octadecyl 3,5-di-t-butyl-4-
Abundance

260000 291
240000
220000
200000
180000
160000
140000
120000
100000
147
219
80000
60000
57
40000
20000 189
91 129
171 249 308
40 74 109 273 341360 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 301 -
OCTADECYL 3,5-DI-T-BUTYL-4-HYDROXYHYDROCINNAMATE
Abundance

530
4500000
4000000
3500000
3000000
2500000
2000000
1500000 219
57
1000000
500000 147 278
97 185 474
317 374 416 564 623 664
697736771
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z-->
Mass spectra of peaks detected when the solvent standards of oleamide were
analysed by GC-MS
TETRADECANAMIDE – impurity in or breakdown product of oleamide

Abundance

59
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
600
41
400 83
112
200 137 225
208 355
154 177
283 401
251 429
311328
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 302 -
TETRADECANAMIDE – impurity in or breakdown product of oleamide
Abundance
Average of 16.692 to 16.749 min.: rxn_060307_023.D

50000
59
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
41
8000
6000
86
4000 128
184 207
2000 227
111 281
156 251 327 355 415
385
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
HEXADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of

oleamide
Abundance

8000 88
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500 57
2000 41
284
1500
157
241
1000 115
199
500 341
141 177 218 308
267 357 403
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 303 -
PENTADECANAMIDE – impurity in or breakdown product of oleamide
Abundance

59
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000 41
86 198
500 114 355
147 170 221
241 281 304325 415
385 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of oleamide

Abundance

10500 55
10000 122
9500
9000
8500
8000
7500
7000
6500
6000
5500 83
5000
4500
4000
3500 150 220
3000
2500
263
178
2000
1500
1000
500 105
198 281 304 341 401
241 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 304 -
OXADECANITRILE – impurity in or breakdown product of oleamide
Abundance

750 72
700
650
600
550 110
500
450
43
400
350
300
150 208
250
180
200
236
150
263
100
91 342
429
50 283
133
314 385
409
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
HEXADECENAMIDE – impurity in or breakdown product of oleamide

Abundance

280000 59
260000
240000
220000
200000
180000
160000
140000
120000
100000
41
80000
60000
40000 126
98
253
20000 154
79 210
192 235
172 281 310 341 383 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 305 -
HEXADECANAMIDE – impurity in or breakdown product of oleamide
Abundance

59
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
200000 41
86 128 212
100000
170 255
109 147 194 237 277 312 342 385403 429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HEPTADECANAMIDE – impurity in or breakdown product of oleamide

Abundance

40000 59
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000 41
6000
128
4000 86
226
2000 170 269
111
153 198 252 326 356 415
308 385 432
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 306 -
HEPTADECENAMIDE – impurity in or breakdown product of oleamide
Abundance

59
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
41
4500
4000
3500
3000
2500 126
81
2000
1500 267
100 147
1000
224
500 168 193
249 327 357 416
295 385 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
OLEAMIDE
Abundance

59
3500000
3000000
2500000
2000000
1500000
41
1000000
126
500000 98 281
79 154 238
184
202220 263 313 338356 385 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 307 -
OCTADECANOIC ACID, BUTYL ESTER – impurity in or breakdown product of
oleamide
Abundance

285
4500
4000
3500
3000
2500
267
56
2000
340
1500
129
1000
241
185
500 108 168
75 212 415
146 323 356 378397
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->
OCTADECANAMIDE – impurity in or breakdown product of oleamide

Abundance

1100000 59
1000000
900000
800000
700000
600000
500000
400000
300000
200000
41 128 240
100000 86
283
184
156 212 261 326 355 383404 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 308 -
DI-(2-ETHYLHEXYL) PHTHALATE – impurity in or breakdown product of oleamide
Abundance

11500 149
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
167
4000
3500
3000
2500
57
2000 279
1500
1000 113
500 83 207 325

131 237255 355 399417
187 297 381 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
ICOSENAMIDE – impurity in or breakdown product of oleamide

Abundance

15000 59
14000
13000
12000
11000
10000
9000
8000
7000
6000
41
5000
4000
3000 81
126
2000
100 309
1000 154
180 212 235 266 290 343 429
369 399
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 309 -
Mass spectra of peaks detected when the solvent standards of titanium dioxide
were analysed by GC-MS
No peaks detected in TIC
Mass spectra of peaks detected when the solvent standards of N,N-bis-(2-

hydroxyethyl)alkyl(C13-C15)amine were analysed by GC-MS
TETRADECANE – impurity in or breakdown product of N-bis-(2-

hydroxyethyl)alkyl(C13-C15)amine
Abundance

57
3500
3000
2500
2000
85
1500
1000
500
113 198
141 281
40 169 253 327 355 401
225 430
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 310 -
2,4-BIS(1,1-DIMETHYLETHYL)PHENOL – impurity in or breakdown product of N-bis-
(2-hydroxyethyl)alkyl(C13-C15)amine
Abundance

191
50000
45000
40000
35000
30000
25000
20000
15000
10000
57
5000
74 91 163
115
40 133 208225 250 281 309327 355 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13-

C15)amine
Abundance

2400 86
2200
2000
1800
1600
1400
1200
1000
800
600
400 56
200
105 238 327 415
133 193 355
152 211 267
284 387
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 311 -
C15)amine
Abundance

86
2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
135
600
400
56
200 107
343
165 194211 234 268 415
251 323 385
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

C15)amine
Abundance

7500 86
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
56
1000
500 224
107 131149 254
40 168 207 282 327 355 401
417
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 312 -
C15)amine
Abundance

7000
86
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
56
1000
500 135
224
112 177 254
154 207 282 341 401 429
370
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

C15)amine
Abundance

100
5000
4500
4000
3500
3000
2500
2000
1500
1000
500 209
163 282
55
79 116134 327 401
192 234253 357 417
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->
- 313 -
C15)amine
Abundance

18000 86
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
254
7000
6000
5000
4000
3000 56
2000
224
1000
112 135 163182 207 281 325
342 429
369 401
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

100
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
341
207
500 269
75
51 415
134
165 189 224 250 296 369 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 314 -
C15)amine
Abundance

174
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000 130 328
500 73 100
43 192 221 253 281 356 416
149 303 387 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

8500 174
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
130
1000
500 328
43 75 107
156 193210 295
228 249268 356 385402 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 315 -
C15)amine
Abundance

19000 86
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000 56
2000
282 341
1000 252
117 140 176196 223
157 373 399 431
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

174
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000 130 328

207
1000
59 85 107 281 401
40 147 224 253 311 356 383 431
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 316 -
C15)amine
Abundance

174
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000 130
328
2000
43 75 102 156 192 224 251 282301 356 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

100
5000
4500
4000
3500
3000
2500
2000
174
1500
1000
144
500 41
328
70 283
125 193 251 357 385 416
221 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 317 -
C15)amine
Abundance

110000 174
100000
90000
80000
70000
60000
50000
40000
30000
20000
130 328
10000
43
75 100 147 200 224242 268 298 345 385403 430
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

C15)amine
Abundance

10500 86
10000
9500
9000
8500
8000
282
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
56
1500
1000
252
500 194 356 430
126145 172 403
107 212 234 300 323 379
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 318 -
C15)amine
Abundance

60000 174
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
130 328
5000
43 75 103 224 251
150 194 281
298 358 383403 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

8000 100
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500 248
2000
1500
1000 207
137 281
500 55 73
399
416
118 161
178 224 298 323342 371 433
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 319 -
C15)amine
Abundance

170000 174
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000 328
20000 114
10000 43 224
86 145 248 270
61 200 298 356 383 415433
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

130000 174
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000
328
20000
130
10000
43 224
75 100 298
154 200 242 270 356 385403 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 320 -
C15)amine
Abundance

8500 174
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
130
1000
281 356
500 57 253 403
77 102 154 211 325
235 299 384 432
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

11000 248
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000 402
1500
1000 133 342

107 204
224
500 43 73 163
282 429
182 304324 360 385
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 321 -
C15)amine
Abundance

114
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500 224
4000
3500
3000
2500 86
2000
1500
1000
58 283
500 140 248
168 196 416
40 309 330 358 386 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

174
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
130 356
4000
2000 207
43 73 281 328
100 151 252 396415
230 310 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 322 -
C15)amine
Abundance

174
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000 356
130
4000
2000 73 207 281

43
100 150 252
235 309327 396 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

60000 174
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000 356
130
5000 207 248
43 73 281
96 154 228 300 326 385404 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 323 -
C15)amine
Abundance

7000
210
6500
6000
5500
5000
4500
4000
3500
154
3000 238
112
2500
2000
1500
188
1000 281
73
500 55 329 396
378 415
92 135 256 307 355
443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

C15)amine
Abundance

210
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
238
4000
3500
168
3000
2500
2000
43
1500
1000 98 140 267

69
500 294 385
322 350 417
118 188 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 324 -
C15)amine
Abundance

210
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000 253
84 281
1500
43
1000 154 179
500 61 112
355 387 429
132 308327
235 404 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of glycerol

monooleate were analysed by GC-MS
TETRADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of

glycerol monooleate
Abundance

88
5000
4500
4000
3500
3000
2500
2000
1500
43
1000 157
70
211
256
500
115
134 177 282
357 415
233 309328 383 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 325 -
HEXADECENOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance

4000 55
3500
3000
88
2500
2000
1500 194
237
111 152
1000
500
282
129 342
175 219 265 311 371 402 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HEXADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol

monooleate
Abundance

9500 88
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
43
2500
284
2000
157
70 241
1500
1000
115 199
500
137 306 343 429
175 219 265 325 367385403 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 326 -
HEPTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of
glycerol monooleate
Abundance

2800 88
2600
2400
2200
2000
1800
1600
117
1400
1200 57
1000
800 157 298
600
211 255
400
185 356
200 327 415
229
136
387 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HEPTADECENOIC ACID, ETHYL ESTER – impurity in or breakdown product of

glycerol monooleate
Abundance

1300 55
1200
1100
1000
900
800 101
83
700
600
250
500
400 211
300 166
133 325
200 296
343
100
185 229 402
269
383 431
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 327 -
LINOLEIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance

67
3000
2500
95
41
2000
1500
1000
123
150 262
500 207
178 308 356
237 282 403
329 385 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
OCTADECENOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol

monooleate
Abundance

260000 55
240000
220000
200000
180000
88
160000
140000 264
120000
100000
222
80000 111
60000 180
40000 137155
310
20000
246
199 282 341 371 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 328 -
OCTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance

88
5500
5000
4500
4000
3500
3000
2500
2000
1500 269 312
157
43
1000
61 213
500 115
139 179 399
241
293 343 371 431
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of glycerol monooleate

Abundance

55
1400
1300
1200
1100
1000
98 207
900
237
800
700
135
600
73
500
401
400
300 269
165
200 355
325
117 185
100 295
429
381 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 329 -
OCTADECENOIC ACID, 2,3-DIHYDROXYPROPYL ESTER – impurity in or breakdown
product of glycerol monooleate
Abundance

55
55000
50000
45000
265
40000 98
35000
30000
25000
20000
15000
137
10000 79 221
174
5000 117 193
155 247 340
283
302322 359 383401 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

131
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
101
4000
3000
75
2000 203
281 355 384
237 429
1000 259
40 173 299 328 403 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 330 -
Abundance

130
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
96
2500 371
2000 239
43
1500
1000 71 315
190
500 281
149 208 259 344 432
172 404
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

131
110000
100000
90000
80000
70000
60000
50000
40000
30000
101
20000 55
75 203 265 412

10000
151 173 221 246 283 316 341 369389 430448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 331 -
Abundance

55000 117
50000
45000
40000
35000
30000
25000 55
20000
15000
98 203
264
10000 75 149 412
339
175
5000
227246 287 315 369388 432
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
CHOLESTA-3,5-DIENE – impurity in or breakdown product of glycerol monooleate

Abundance

368
5500
5000
4500
4000
3500
3000
2500
145
43 81
2000
117
247
1500
213 400
1000
500 285
163 323 445
190
345
62 99 419
304
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 332 -
Mass spectra of peaks detected when the solvent standards of sodium (C10-C18)
alkyl sulfonate were analysed by GC-MS
TETRADECANE – impurity in or breakdown product of sodium (C10-C18) alkyl

sulfonate
Abundance

4500 57
4000
3500
3000
2500
2000 85
1500
1000
500
113 198
133
155 253 283 342 401 429
177 221 369
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PENTADECANE – impurity in or breakdown product of sodium (C10-C18) alkyl

sulfonate
Abundance

16000 57
15000
14000
13000
12000
11000
10000
9000
85
8000
7000
6000
5000
4000
3000
2000
212
112
1000 141 169 191
40 251 282 325
342 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 333 -
HEXADECANE – impurity in or breakdown product of sodium (C10-C18) alkyl
sulfonate
Abundance

14000 57
13000
12000
11000
10000
9000
8000
85
7000
6000
5000
4000
3000
2000
113 226
1000 141 208
169
251 282 327 356 387 415 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HEPTADECANE – impurity in or breakdown product of sodium (C10-C18) alkyl

sulfonate
Abundance

57
12500
12000
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500 85
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
113 240
1000
141
500 183 209 327
267 355 416
163 295 387 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 334 -
Mass spectra of peaks detected when the solvent standards of 2,5-bis(5'-tert-
butylbenzoxazol-2-yl)thiophene were analysed by GC-MS
2,5-BIS(5'-TERT-BUTYLBENZOXAZOL-2-YL)THIOPHENE
Abundance
Average of 31.514 to 31.909 min.: Average of 30.031 to 31.243 min.: rxn_060307_ (+)
430
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
207
600000
400000
105
73 172 281
133
387
200000 359
239 341
41
151 263 299318 405 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 335 -
PEAKS DETECTED IN THE CHROMATOGRAMS OF THE PS ADDITIVES
Mass spectra of peaks detected when the solvent standards of

ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) were
analysed by GC-MS
UNKNOWN – impurity in or breakdown product of ethylenebis(oxyethylene)bis-(3-(5-

tert-butyl-4-hydroxy-m-tolyl)-propionate)
Abundance

161
85000
80000
75000
235
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
91 128
5000 41 74 178
207
108 252 281 327 357 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 336 -
Abundance

175
5500
5000
4500
4000
278
3500
3000
2500
2000
1500
1000 145
500 91 128 192

57 217
249 327 415

74 109 356 389
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
3-METHYL-5-TERT-BUTYL-4-HYDROXYPHENYL ETHYLPROPANOATE – impurity in

or breakdown product of ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-
tolyl)-propionate)
Abundance

1100000 161
1000000
900000
800000
249
700000
600000
500000
400000
300000
200000
100000 91 128 190

57
221
109 267 295
313 341
359 383401 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 337 -
Abundance

291
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500 147 219
2000
57
88
1500
1000
177
500 129
109 199 241 267 325343 369 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

9500 161
190
9000
8500
8000
7500
7000
6500
6000
5500
5000 368
4500
4000
3500
45
3000
2500
2000
1500 247
1000 87
105 128
500 328
217 285
65 309 346 389 417 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 338 -
Mass spectra of peaks detected when the solvent standards of tris(nonylphenyl)
phosphite were analysed by GC-MS
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite

Abundance

107
8000
7500
7000
6500
135
6000
5500
5000
4500
4000
3500
3000
2500
2000 220
1500
57 191
1000
77
500
40 163 282 341 415
251 313 369389
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

107
3000
2500
2000 135
1500
71
1000
220
500 355
43 191
281
89 163
327 401
251 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 339 -
Abundance

121
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000 163
220
43 91
500
341
69 191
147 282
253 325 416
367387
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

6000 107
5500
5000
4500
4000
3500
3000
2500
2000
1500
220
1000
150
91
500 177
43
71 267
131 342
249 325 416
195 385
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 340 -
Abundance

210000 135
200000
190000
180000
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000 107
40000
30000
20000
41
10000 77 177 220
59 157 195 251270 296 327 355 401

383 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphate

Abundance

121
450000
400000
350000
300000
250000
163
200000
150000
100000
50000 41 220
91
65
145 193 253 281
299 327 357 383401 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 341 -
Abundance

135
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000 107
41 220
77
59 161 189 249 283 313 341 383
401 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

149
2000000
1800000
1600000
107
1400000
1200000
1000000
800000 191
600000
400000
220
55
200000 77
131
173 265283 325
343 369389 416 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 342 -
Abundance

135
1600000
1400000
1200000
1000000
800000
107
600000
400000
200000 220
41 191
77
59 161 249 279 313 341 371 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

2200000 135
2000000
1800000
1600000
1400000
1200000
1000000
107
800000
600000
400000
191 220
200000 41
77
59 163 253 281 305 329 355 386 417 445

0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 343 -
Abundance

107
600000
163
550000
500000
450000
400000
350000
135
300000
250000
200000
150000
100000
41 77 220
50000
60 181 203 251 282 342

325 368 415 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

149
900000
800000
700000
107
600000
500000
400000
177
300000
200000
100000 55
77
220
131
195 253 281 311
328 356 383401 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 344 -
Abundance

135
4000000
3500000
3000000
2500000
2000000
1500000
1000000
107
500000
41
77 220
58 161 191 251 281 325 356374 401 430
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

149
900000
800000
700000
600000 107
500000
400000
300000
200000
191
100000 55
77 220
131
171 251 283 327 356 383401 429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 345 -
Abundance

60000 135
55000
50000
45000
40000
35000
30000
25000
20000
15000 107
10000 163
234
5000 41 191
77
58 210 269
252 295 328 367387 417
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

190000 135
180000
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
107
40000
30000
20000
41
163 234
10000 77
191
59 209 265283 325 357 387 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 346 -
Abundance

36000 161
34000
32000
30000
28000
26000
24000
249
22000
20000
18000
16000
14000
12000
10000
8000
6000
135
4000 91
57 115 190
2000
221 282 307 329 355 387 415
432
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

291
26000
25000
24000
23000
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000 147 219
8000
7000
6000 57
5000
4000 88
3000
2000 189
129
1000 105
171 239 263 308
40 343
326 371 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 347 -
Abundance

255
15000
14000
13000
12000
11000
121
10000
9000
8000
7000
6000 93
5000
65
4000
3000 340
2000
163
41 279
1000 181
208227 311
145 357 387 415
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

121 283
32000
30000
28000
26000
24000
22000
20000
18000
16000 93
14000
65
12000
10000
241
8000
6000
340
4000
43 149
167
2000
191209 264 313 401
358 384 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 348 -
Abundance

255
360000
340000
320000
300000
280000
260000
240000
220000
200000
180000 121
160000
140000
120000
100000 93
80000
65
60000
340
40000
43 163
20000
181
227 295
141 199 274 312 357 387 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

269
220000
200000
180000
311
160000
140000
121
120000
100000
80000 93
60000 65
40000
340
20000 149 177
43 237
195213 293 373 399 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 349 -
Abundance

121
150000
140000
269
130000
120000
110000
100000
90000
93
80000
70000
65
60000
311
50000
40000
241
30000 340
20000
43
149 177
10000
195213
293 358 385402 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

255
200000
121
190000
180000
170000
160000
150000
140000
130000
120000
110000
93
100000
90000
80000 65
70000
60000
311
50000
340
40000
30000
20000
163
41
10000 181
227
141 199 283 371390 417 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 350 -
Abundance

140000 269
121
130000
120000
110000
100000
90000
297
80000
70000
60000 93
50000 65
40000
30000
20000
43
177
10000 153 241
195 223 340
322 358 385 415 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

110000 283
100000
90000
80000
121
70000
60000
50000
40000
93
30000 65
20000
10000 255 325

41 149167 191 227 354
209 387 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 351 -
Abundance

255
500000
450000
400000
350000
300000 121
250000
200000
150000
93
65
100000
311
50000 163
43
181 283 340
141 199 227 385403 431
449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

269
140000
130000
120000
121
110000
100000
90000
80000
70000
60000 93
50000
65
40000
30000
20000 340
43 177
10000 153
227 295
195
251 323 367385 415433
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 352 -
Abundance

30000 255
28000
26000
24000
22000
20000
18000
16000
121
14000
12000
10000
93
8000
6000 65
4000 283
354
43 163
2000 181
145 207227 309328 385403 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

20000 255
19000
18000
17000
16000
15000
14000
13000
12000
11000
121
10000
9000
8000
7000
6000
93
5000
4000 65
3000
2000 325
43 354
163
207
1000 181
227 281
141 298 387 416
433
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 353 -
Abundance

18000 255
17000
16000
15000
14000
13000
12000 121
11000
10000
9000
8000
7000
6000 297
93
5000
65
4000
3000
2000
41 163 325
1000 181 354
141 213233 279 385 416 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

7000
121
6500 255
6000 297
5500
5000
4500
4000
3500
93
3000
65
2500
2000
1500
354
1000
153
500 43 181
205 227 279 324 388
416
446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 354 -
Abundance

25000 255
24000
23000
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000 121
8000
7000
6000
5000
4000
93
65
3000
2000 163
1000 41
289 354
141 181201221 309327 402 430
383
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

90000 429
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
71
20000
15000
181
295
10000 43
135
5000 107 153 207
341
89 232251
269 314 359 388 411 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 355 -
Abundance

85000 429
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000 71
20000
15000
172
10000 43 295
107 153
5000 135
195
89 219237 265 331 357 383401 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

120000 429
110000
100000
90000
80000
71
70000
60000
50000
165
43
40000 295
30000
107127
20000
10000 207
147 186
89 237 265 317 341 369 401 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 356 -
Abundance

429
105000
100000
95000
90000
85000
80000
75000
70000
65000
60000 71
55000
50000
45000
40000 165
35000
30000 43 295
25000
20000
107
15000 127
10000
209
5000
186
145 265 343 365385
89 239 317 411 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

429
1000000
900000
800000
700000
600000
500000
400000
71
300000
200000
43 181 295
100000 158
107127
89 209 237 265 317 343361 383401 447

0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 357 -
Abundance

429
900000
800000
700000
600000
500000
400000 71
300000
200000 43 295
172
153
107127
100000
195
89 219237 265 317 343361 383401 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

650000 443
600000
550000
500000
450000
400000
350000
300000
250000 71
200000
295
150000
43 165
100000
107127
50000
195 415
89 145 237 265 317 343 369
219 387
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 358 -
Abundance

443
130000
120000
110000
100000
90000
80000
70000
71
60000
50000
40000
158
30000 295
43
107
20000 127
179
10000 223
89 205 267 329 369 425
249 347 387
405
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

429
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000 71
60000 181
43
40000
295
107 135153
20000
89 209 317337 359 383
230249267 411 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 359 -
Abundance

429
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000 71 181
43 295
135
91 117 163
209 237 265 317 343 365383401 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

429
1000000
900000
800000
700000
600000
500000
400000
300000
200000
71
181
100000 43 295
107127 153
89 209 237 265 317 343 371 401 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 360 -
Abundance

550000 429
500000
450000
400000
350000
300000
250000
200000
150000 71
100000
43
181 295
153
50000 107127
89 209 237 265 331 357 381399

313 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

443
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000 71
60000
43 181
40000
153 295
107127
20000
209 415
89 237 265 317338357 385
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 361 -
Abundance

429
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000
71 181
20000 43
127 153 295
107
208 230251 277 327345 368 399 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

429
450000
400000
350000
300000
250000
200000
150000
100000
71
181
43
50000 295
135
153
107
89 211 237 265 324343 371 398 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 362 -
Abundance

443
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
71
5000 43 207
153 181
107 135 309 341
238 267 289 368 401419
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

443
60000
55000
50000
45000
40000
35000
30000
25000
20000
71
15000
43 181
10000
135
153
107 295
5000
89 200 223 247 274 313 343 373 396415

0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 363 -
Abundance

177
900000
800000
700000
600000
500000 368
400000
300000
217
200000
57 263
100000 87
121 147
236 312 350
199 281 330 401 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of di-(2-ethylhexyl)

phthalate were analysed by GC-MS
UNKNOWN – impurity in or breakdown product of di-(2-ethylhexyl) phthalate

Abundance

161
2200
2000
1800
1600
249
1400
1200
1000
800
600
400 133
91 207
200 73 282 341
115 401
53 429
179 304323 371 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 364 -
UNKNOWN – impurity in or breakdown product of di-(2-ethylhexyl) phthalate
Abundance

291
550
500
450
207
400
350
101
300
250 147
78
57
200
121
150
343
100
267 325
50 239
185 401
40
165 429
383
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of di (2-ethylhexyl) phthalate

Abundance

149
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
177
15000
195
10000
70
5000 41
104
122 221 251 282 306327 355 387 415 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 365 -
DEHP ISOMER – impurity in or breakdown product of di-(2-ethylhexyl) phthalate
Abundance

6000 149
5500
5000
4500
4000
3500
3000
2500
167
2000
1500
57
1000
500 113 279

76 415
195 223 251 328 357
94 131 311 385 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
DEHP ISOMER – impurity in or breakdown product of di-(2-ethylhexyl) phthalate

Abundance

149
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
167
18000
16000
14000
57
12000
10000
279
8000
6000 113
4000
83
2000
131 186205 231251 311 342 365 399 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 366 -
DEHP – impurity in or breakdown product of di-(2-ethylhexyl) phthalate
Abundance

149
3000000
167
2800000
2600000
2400000
2200000
2000000
1800000
279
1600000
57
1400000
1200000
1000000
800000
113
600000
83
400000
200000
261 391 416

185203221 242 304 334 361 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of N,N-

bis(stearoyl)ethylenediamide were analysed by GC-MS
No peaks detected
- 367 -
Mass spectra of peaks detected when the solvent standards of polyethylene
glycol 4-tert-octyl-phenyl ether, n~5 were analysed by GC-MS
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octyl-

phenyl ether, n~5
Abundance

75000 179
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000 135
20000
15000
10000
107
5000 57 250
77
40 161 207 233 281 327 355 387 415
432
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

phenyl ether, n~5
Abundance

235
4000
3500
3000
2500
2000
135
1500
1000 44 191
500
207
115 306
78 175
97 159 281 327 355
253 401
0
40 60 80 100120140160180200220240260280300320340360380400
m/z-->
- 368 -
phenyl ether, n~5
Abundance

135
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
247
3000
2500
2000
1500
57
1000
107
318
500 179
40 77 161 209 281 341 415
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

phenyl ether, n~5
Abundance

119
161
4500
4000
223
3500
3000
2500
45
2000
91
1500
1000 294
500
205
65 137 179
341
269 400 429
251
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 369 -
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY) ETHANOL – impurity in
or breakdown product of polyethylene glycol 4-tert-octyl-phenyl ether, n~5
Abundance

220000 223
200000
180000
160000
140000
120000
100000 135
80000
60000
40000
45
20000 107 294
77 161179 205 249267 313 341 369387 415 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

phenyl ether, n~5
Abundance

42000 223
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000 135
18000
16000
14000
12000
10000
8000
6000 45
4000 107
2000
77 161 265
179 205 247 294 327 355 399 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 370 -
phenyl ether, n~5
Abundance

57
4500
161
279
4000
3500
3000
2500 217
2000 350
119
1500
1000
500 91 191
136
247 401
74 311329 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

phenyl ether, n~5
Abundance

291
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000 57
8000
6000
4000
175 247 362
2000 147
119 219
91 194 267 324342 401 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 371 -
phenyl ether, n~5
Abundance

8000 279
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000 191
2500
2000
1500
1000 57
350
136
500
95 115 161 210229249 401 429
75 297 328 371
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

phenyl ether, n~5
Abundance

161
4000
3500
3000 45 119
2500
267
2000
1500 87
1000
500 338
207 359
69 181 415
139 237
292310 385 432
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 372 -
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY) ETHANOL LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octyl-
phenyl ether, n~5
Abundance

11000
267
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
45
3000 135
2500
2000
1500
89
1000 161
338
500 107
67 179 205 402 429
237 293313 358 383 446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

phenyl ether, n~5
Abundance

335
50000
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000 57
267
14000
12000
10000
8000 161
247
6000
135 406
4000
89 189
2000 107 217
295 356
317 387 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 373 -
phenyl ether, n~5
Abundance

311
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
45
14000
12000
10000
135
8000
89
6000 161
4000
107 382
2000
67 205
179 223 252 279 339358 400418 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

phenyl ether, n~5
Abundance

379
30000
28000
26000
24000
22000
20000
18000
16000
14000
57
12000
10000
8000
6000 161
247
4000 273 311
89 133 207
189
2000
113 291 339 415435
229 358
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 374 -
COMPOUND - impurity in or breakdown product of polyethylene glycol 4-tert-octyl-
phenyl ether, n~5
Abundance

22000 355
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
45
11000
10000
9000
8000
7000
6000 161
89 135
5000
4000
3000
2000 426
107 205
1000 71 311
187 223 445
241259 289 337 384405
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

phenyl ether, n~5
Abundance

75000 399
70000
65000
60000
55000
50000
45
45000
40000
35000
30000
89 161
25000
20000
135
15000
10000 205
5000 107
311 369
67 187 223 249267 293 337 418 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 375 -
Mass spectra of peaks detected when the solvent standards of polyethylene
glycol 4-tert-octyl-phenyl ether, n=9-10 were analysed by GC-MS

phenyl ether, n=9-10
Abundance

19000 267
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
45 135
5000
4000
3000
89
2000
161
107 338
1000
67 179 205223 415
249 311 357 387
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

70000 311
65000
60000
55000
50000
45000
40000
35000
30000
25000 45
20000
15000 135
89
10000 161
5000 382
107 205 415
67 179 223 249267285 339358 432
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 376 -
Abundance

140000 355
130000
120000
110000
100000
90000
80000
70000
45
60000
50000
40000
89 161
30000 135
20000
10000 205 426

107
67 179 223 249
267 293 325
378397 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

399
38000
36000
34000
32000
30000
28000
26000 45
24000
22000
20000
18000
16000
89 161
14000
12000
10000
8000 135
6000
205
4000
2000 107
67 187 223 249 297 326
369 419 441
277 345
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 377 -
Abundance

45
4500
443
4000
3500
207
3000
89
161
2500
133
2000
1500
281
355
1000
249
415
500 107
179 325
67 299 381
230
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of 2-(2’-hydroxy-5’-

methylphenyl) benzotriazole were analysed by GC-MS
2-(2’-HYDROXY-5’-METHYLPHENYL) BENZOTRIAZOLE
Abundance

850000 225
800000
750000
700000
650000
600000
550000
500000
450000
400000
350000
300000
93
250000
168
200000
65
150000 196
100000
50000 113
41 141
253 283302 328 356 401
383 429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 378 -
PEAKS DETECTED IN THE CHROMATOGRAMS OF THE PET ADDITIVES
Mass spectra of peaks detected when the solvent standards of 2-(2H-

benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol were analysed by GC-
MS
2-(2H-BENZOTRIAZOLE-2-YL)-4,6-BIS(1-METHYL-1-PHENYLETHYL)PHENOL
Abundance

432
1600000
1400000
1200000
1000000
800000
600000
400000 342
91
119
200000
41 165 370
207
65 141 189 228 252 281 314 388406
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of hexanedioic acid
polymer with 1,3-benzenedimethanamine were analysed by GC-MS
No peaks detected
- 379 -
Mass spectra of peaks detected when the solvent standards of copper
phthalocyanine blue were analysed by GC-MS
1,1-DIMETHYLPENTYL BENZENE – impurity in or breakdown product of copper

phthalocyanine blue
Abundance

119
4000
3500
3000
2500
91
2000
1500
1000
500 56 176
147
73
207 251 281 341 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 380 -
PEAKS DETECTED IN THE CHROMATOGRAMS OF THE PVC ADDITIVES
Mass spectra of peaks detected when the solvent standards of dioctyltin

bis(ethylmaleate) were analysed by GC-MS
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)

Abundance

3000 341
2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
45
600
73
163
400 267
207
200 135 295
91 237
117 416
181 359 389
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
SILICIC ACID, DIETHYL BIS(1-METHYLSILYL) ESTER – impurity in or breakdown

product of dioctyltin bis(ethylmaleate)
Abundance

32000 207
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
237
6000 281
4000
2000 133 177

73 96 115
45 150 254 299 327 356 416
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 381 -
Abundance

341
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
73
163
500 193
133 221 295
54 98 269 415
252 313 358 385
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
DECAMETHYL CYCLOPETASILOXANE – impurity in or breakdown product of

dioctyltin bis(ethylmaleate)
Abundance

5000 355
4500
4000
3500
73 267
3000
2500
2000
1500
1000
113
500
191 249 323
45 96 209
133 162 295 429
401
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 382 -
Abundance

237 267
2800
2600
2400
2200
2000
1800
1600
1400
1200
193
1000 137
800
155
600
355
400
119
200 211
46 78 295 327
96
176 385 417 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
2-BUTENEDIOIC ACID (Z)-, METHYL ESTER – impurity in or breakdown product of

dioctyltin bis(ethylmaleate)
Abundance

99
600000
550000
500000
450000
400000
350000
300000
250000
200000 127
150000
100000
50000 54 82
145 172189207 249 282 323341 371 401 429

0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 383 -
Abundance

2000 193
237
1800
1600
1400
1200
1000
800 99
600
119 211
281
400
45 81 311
200 255
143 165 342
415
385
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

1600 269
1500
1400
1300
1200
1100
1000
900
800 133
700
600
500
151 193
400
250
100
300
75 311
200 175
223
58 286 341
100 41
431
369 404
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 384 -
Abundance

415
2800
327
2600
2400
2200
2000
1800
1600
1400 73
1200
1000
800
600
400 399
99 127
45 147 179
200
268 295
208 251
225 355
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->

Abundance

4500 193
4000
3500
3000 237
2500
2000
1500
1000
279
500
135
163 353
115
89
40 63 211 326 401
297 431
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 385 -
Abundance

4000 193
3500
3000
237
2500
2000
1500
1000
133
500 163
105 279
45 74 342
325
210 415
254 297 369
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

281
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
355
2000 251
207
1000 73 191
55 103 133 325
165 223 297 399415
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->
- 386 -
Abundance

355
7500
7000
6500
6000
5500
5000 73 177
4500
4000
267
3500
3000
2500
2000
1500
325
1000
429
500 133
55 96 207 249
150 229 293 399
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

161
16000
15000
14000
203
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000 91
41 115
2000 134
65
1000
185 220 341 401
237 265 293313 427
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 387 -
BUTYLATED HYDROXYTOLUENE – impurity in or breakdown product of dioctyltin
bis(ethylmaleate)
Abundance

4500000 205
4000000
3500000
3000000
2500000
2000000
1500000
1000000
57 145
500000 177
105
81
127 223 267 295313 341 387 415 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
BRANCHED ALKANE – impurity in or breakdown product of dioctyltin bis(ethylmaleate)

Abundance

57
3500
3000
2500
2000
85
1500
112
1000 140
500
207
268 355 415
161 189 226 249 295 328 387 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 388 -
Abundance

69
1600
1400
1200
1000
111
41
800
224
600
400
129
91 177
200 415
154 199 343
265
282 385
311
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
HEXADECANE – impurity in or breakdown product of dioctyltin bis(ethylmaleate)

Abundance

57
14000
13000
12000
11000
10000
9000
8000 85
7000
6000
5000
4000
3000
2000
113 226 341
1000 141 177 251 429
40 159 197 282 323 383401
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 389 -
1,1’-OXYBISBENZENE – impurity in or breakdown product of dioctyltin
bis(ethylmaleate)
Abundance

30000 71
28000
26000
24000
22000
20000
18000
16000
43
14000
12000
10000
8000
6000 112
4000
2000 208
131
95 149 177 226 249267
284 309327 355 387 415
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

Abundance

207
16000
15000
14000
13000
12000
133
11000
10000
9000
8000 151
7000
281
6000
5000
4000
3000
2000 73
1000 341
45 96 177 251
115 225 415
309 359 383 439
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 390 -
Abundance

10500 207
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
43 343
133
4500
4000 151
3500 281
3000
249
2500
2000
70
1500
1000 325
96 361
401
500 174
115 225 381 419 441
305
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of dioctyltin bis(2-
ethylhexyl thioglycolate) were analysed by GC-MS
2-ETHYL-1-HEXANOL – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl

thioglycolate)
Abundance

450000 57
400000
350000
300000
250000
200000
150000
83
100000
50000
112
40 129147 177 207225 253 281 311 341 370 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 391 -
2-ETHYLHEXYL MERCAPTOACETATE – impurity in or breakdown product of
dioctyltin bis(2-ethylhexyl thioglycolate)
Abundance

190000 57
180000
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
112
50000
40000
30000
83
20000
145
10000
175 207225 251 281 311 341 369387 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
2,4-BIS(1,1-DIMETHYLETHYL)PHENOL – impurity in or breakdown product of

Abundance

28000 191
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000
2000 74 91 115 163

47 133 209 239 267285 325343 387 416
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 392 -
BRANCHED ALKANE – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance

71
6500
6000
5500
5000
4500
43
4000
3500
3000
99
2500 182
2000
1500
1000
127
500
154
269 342
211 251 295 325 401 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

thioglycolate)
Abundance

57
4500
4000
3500
85
3000
2500
2000
197
1500
1000
154
112
500
267
221 343 401

135 249
175 284 309
326 383 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 393 -
thioglycolate)
Abundance

57
7500
7000
6500
6000
5500
5000
4500
4000
85
3500
3000
2500
112
140
2000
1500
1000
500 211
182 251 283 342 415
40 163 313 388
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl

thioglycolate)
Abundance

129
7000
73
6500
6000
5500
5000
4500
4000
3500
55
3000
199
2500
2000
1500
1000
500 97
281
149169 222 251 327 355 401 432
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 394 -
HEXADECANE – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance

57
105000
100000
95000
90000
85000
80000
75000
70000
65000
60000
55000 85
50000
45000
40000
35000
30000
25000
20000
15000
10000 113 226
5000 141
169
197 341 415
253271 295 323 369
387 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
1,1’-OXYBIS OCTANE LIKE COMPOUND – impurity in or breakdown product of

Abundance

71
150000
140000
130000
120000
110000
100000
90000
80000
43
70000
60000
50000
40000
30000 112
20000
10000
131
95 157 185 209 241 265
282 341 369 397415
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 395 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance

57
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
164
10000 182
9000
8000
7000 276
6000 406
5000
112
4000
137
3000
83
2000 294
1000
204 250 342
222 325 361 387 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of epoxidised soya
bean oil were analysed by GC-MS
HEXADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of

epoxidised soya bean oil
Abundance

88
12000
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500 43
3000
2500 284
157
2000 70 241
1500
1000 115 199

500 135 221 355
177 265 306325 383 415 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 396 -
OCTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of
Abundance

4000 88
3500
3000
2500
2000
1500 43
312
1000 69
269
157
133
207
500
115
357 401
227 251 430
185 293 383
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
trans-9,10-EPOXYOCTADECANOIC ACID – impurity in or breakdown product of

Abundance

7000 55 155
6500
6000
5500
5000 88
4500
4000
3500
3000
2500 109
2000
1500
185
213
1000
136
500 415
241 265 295 329 357
383 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 397 -
UNKNOWN – impurity in or breakdown product of epoxidised soya bean oil
Abundance

130
3500
3000
2500
2000
1500
1000 371
43 239
101
71 429
500 315
149 194
401
176 221 259 284 343
448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
EPOXIDISED FATTY ACID – impurity in or breakdown product of epoxidised soya

bean oil
Abundance

11500 155
11000
10500
10000
9500
9000 55
8500
8000
7500
7000
6500
6000
5500 83
5000
4500
109
4000
3500
3000
2500
2000
1500
1000 137 194

500
213 265 295 430
175 239 322 357 385403
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 398 -
EPOXIDISED FATTY ACID – impurity in or breakdown product of epoxidised soya
bean oil
Abundance

4500 155
4000
3500 55
3000
2500
83
2000
1500 109
1000
221
265
500
137 356
201
175 295 417
239 328 385
446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of stearic acid were
analysed by GC-MS
HEXADECANOIC ACID – impurity in or breakdown product of stearic acid

Abundance

3200
60
3000
2800
2600
2400
256
2200
41
2000 129
1800
1600
213
1400
96
1200
1000
800 157
600 185
429
356
400
200 328
285
401
79 238 309 384
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 399 -
STEARIC ACID
Abundance

73 284
450000 43
400000
350000
129
300000
250000 241
200000 185
97
150000
100000
50000 157 213

312
265 330 355 379399417 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of acetyl tributyl
citrate were analysed by GC-MS
UNKNOWN – impurity in or breakdown product of acetyl tributyl citrate

Abundance

157
85000
80000
75000 231
70000 185
65000
60000
55000
50000
45000
40000
35000
43
30000
25000 129
20000
15000
10000
111 301
5000 273
85 213 329
61
253 355 383401 430
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 400 -
BUTYL CITRATE – impurity in or breakdown product of acetyl tributyl citrate
Abundance

185
6500
6000
5500
5000
4500
4000
3500
259
3000 129
2500 157
2000 43
1500
1000 231
111 301
500 87 283 327
67 207 356 379 415
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of acetyl tributyl citrate

Abundance

1400 185
1300
1200
1100
129
1000
900
41
800
245
700
600
500
400
157 273
300
327
200 203
112
58 87
100
356 415
221 295
385
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 401 -
1-PROPENE-1,2,3-TRICARBOXYLIC ACID, TRIBUTYL ESTER – impurity in or
breakdown product of acetyl tributyl citrate
Abundance

112
157
170000
160000
150000
140000
130000
120000
110000
57
100000
139
90000
80000
70000
60000
50000 213
269
40000
30000
20000 84
185
10000 241
287 342
313 369 402 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->

Abundance

30000 112 157
28000
26000
24000
22000
20000
57
18000
139
16000
14000
12000
10000
213
8000
269
6000
4000 84
2000 185
241
287 313 342 369 402 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 402 -
Abundance

112 157
46000
44000
42000
40000
38000
36000
34000
32000
57
30000
28000
26000 139
24000
22000
20000
18000 185
16000
14000 213
12000
269
10000
8000
6000 84
4000
241
2000
287
313 342 371 401 431
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
ATBC
Abundance

7000000 185
6500000
259
6000000
5500000
129
5000000
4500000
4000000
3500000
3000000
2500000
43
2000000
157
1500000
329
1000000 213
111
500000 87
61 231 301 347 373
277 403 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 403 -
Mass spectra of peaks detected when the solvent standards of paraffin wax were
analysed by GC-MS
The mass spectra are not reproduced here, a series of straight chain, branched and
cyclic alkanes were detected. The TIC is shown below:
Abundance
TIC: rxn_060307_016.D
2.5e+07
2e+07
1.5e+07
1e+07
5000000
4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.0028.0030.00

Time-->
- 404 -
PEAKS DETECTED IN THE CHROMATOGRAMS OF THE PA ADDITIVES
Mass spectra of peaks detected when the solvent standards of zinc stearate were
analysed by GC-MS
No peaks detected
Mass spectra of peaks detected when the solvent standards of talc were
analysed by GC-MS
No peaks detected
- 405 -
ANNEX 2
Mass spectra of each substance detected in the
plastic + additive samples that were not present
in the plastic only control samples
- 406 -
Mass spectra of the peaks detected in the extracts of the PP + additive samples
that were not present in the PP samples
Codes correspond to Table 18 in the main report
PP1
Abundance
Scan 224 (6.899 min): FSA_199.D (-208) (-)

43 61
12500
12000
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
31
5000
4500
4000
3500
3000
2500
2000 15
1500
1000
27
500 19
46 55 73 89
3740 51 58 6568 7780 84 94
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
m/z-->
PP2
Abundance
Scan 392 (8.516 min): FSA_015.D (-386) (-)

4800 115
4600
4400
4200
4000
3800
3600
3400
3200
3000
2800
2600
2400
2200
59
2000
1800
1600
28
1400
1200
1000
800
600
400
416
200 201 267 492
150 299337 574 620656 696 735
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
- 407 -
PP3
Abundance
Scan 515 (9.593 min): FSA_015.D (-510) (-)

91 120
5500
5000
4500
4000
3500
3000
2500
2000
65
1500
1000
51
29
500 39 74
150
84 104 113 128 136
17
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
m/z-->
PP4
Abundance
Scan 584 (10.197 min): FSA_015.D (-580) (-)

4200 140
4000 83
3800
3600
3400
3200
3000
2800
2600
2400 42
2200
2000
1800
1600
1400
1200
1000
800
600
400
274
191229 329 389 474509
200 551 593628
421 681 739
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
- 408 -
PP5
Abundance
Scan 1027 (13.929 min): FSA_199.D (-1035) (-)

70
3000
2800
2600
2400 43
2200 168
152
2000
1800
1600
1400
1200
1000
800
600
96
400 27
124
200
200 249 327 376

0
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380
m/z-->
PP6
Abundance
Scan 1191 (15.365 min): FSA_199.D (-1186) (-)

46000 161
44000
42000
40000
38000
36000
34000
32000
30000
203
28000
26000
24000
22000
20000
18000
91
16000
14000
12000
128
10000
8000
6000
51
4000
2000
15
279 506 716
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
- 409 -
PP7
Abundance
Scan 1240 (15.941 min): FSA_015.D

191
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000 57 91 206
41 115 179
77 105 163
5000 28 128 147
15 67 138
0
0 20 40 60 80 100 120 140 160 180 200
m/z-->
PP8
Abundance
Scan 1393 (17.280 min): FSA_015.D (-1387) (-)

170
4500
4000
3500
102
3000
2500
2000
30
1500
1000
67
500
136 297 621

248 423
371 486
552588 729 771
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 410 -
PP9
Abundance
Scan 1609 (19.025 min): FSA_199.D (-1604) (-)

88
40000
35000
30000
25000 101
20000
15000
10000
73
61 157
5000 29
45
213
115
129 143 171
17 185 199 227 241 256
0
20 40 60 80 100 120 140 160 180 200 220 240 260
m/z-->
PP10
Abundance
Scan 1749 (20.397 min): FSA_015.D (-1755) (-)

175
2400
2200
2000
1800
1600
1400 217
1200 91
1000
57 133
800
600 261
400
200
15 495 766
295 402 563 614 670
327
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 411 -
PP11
Abundance
Scan 1775 (20.625 min): FSA_015.D (-1771) (-)

24000 277
23000
22000
21000
147
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
57
9000
219
8000
7000
6000 91
5000
4000
185
3000
2000
1000
18 463
313 355 429 538579 717 767
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z-->
PP12
Abundance
Scan 1812 (20.802 min): FSA_199.D

150000 43
140000
130000
57
120000
110000
100000 73
90000
80000
70000
60000
50000
40000 29 85 129
30000 97
20000 111
157171185 213
10000 256
143 199 227
15 239 270
0 20 40 60 80 100 120 140 160 180 200 220 240 260
m/z-->
- 412 -
PP13
Abundance
Average of 21.238 to 21.247 min.: FSA_015.D (-)

16000 147
15000 291
14000
13000
12000
11000
10000
9000
8000 57
7000 219
6000
5000
4000
91
3000 187
2000
1000
19 251 348383 430468504 549 612 681716755
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP14
Abundance
Scan 2033 (22.737 min): FSA_199.D (-1993) (-)

43
180000
170000
160000 57
150000
140000
130000
73
120000
110000
100000
90000
80000
70000
60000 129
50000 85
29 97
40000
30000
111 185
20000 241 284
10000 143 171 199
15
157 213227 255269
20 40 60 80 100 120 140 160 180 200 220 240 260 280
m/z-->
- 413 -
PP15
Abundance
Scan 2056 (23.085 min): FSA_015.D

88
70000
60000
50000
40000
30000
43
20000
29 69 157
10000
102 143
269 312
15
129 171185199213227241255 283
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
m/z-->
PP16
Abundance
Scan 2090 (23.236 min): FSA_199.D (-2099) (-)

140000 168
120000
70
100000
80000
60000
284
40000 102
41
20000
138
200227255 319 357 415 509 624
0
0 50 100 150 200 250 300 350 400 450 500 550 600
m/z-->
- 414 -
PP17
Abundance
Scan 2105 (23.514 min): FSA_015.D (-2101) (-)

170
5600
5400
5200
5000
4800
4600
4400
4200
4000
3800
3600
3400
3200
3000
2800
2600
2400 300
2200
84
2000
1800
1600
1400
115
1200
30
1000
800
600 216
400
248
200 356
386 520
421
451 614 670 715
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
PP18
Abundance
Scan 1883 (21.424 min): FSA_091.D (-1880) (-)

43
26000
24000
22000
20000
18000
16000
57
14000
98
12000
10000
8000 84
239
116
6000
4000 29
2000
137 154 182196
15 168 211
225 253 281
267 312 333
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
m/z-->
- 415 -
PP19
Abundance
Scan 1929 (21.827 min): FSA_091.D

34000 57
32000
30000
28000
26000
24000
22000
20000
18000
129
16000 98
14000
12000
10000
8000
6000
4000 185
18
2000 239
283 341374
404 473 568 698
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
PP20
Abundance
Scan 2154 (23.943 min): FSA_015.D (-2141) (-)

117
4000
3500
3000
2500
2000
1500
1000
73 285
211
500
155 464 736 784
18 342 403 683
250 526 591
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 416 -
PP21
Abundance
Scan 2166 (24.048 min): FSA_015.D

10000 43
9000 98
8000
74
7000
211
6000
57
5000
134
4000 29
3000 112
2000
229
154
1000 16 168 271
185 242
297
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
m/z-->
PP22
Abundance
Scan 2221 (24.530 min): FSA_015.D (-2227) (-)

72
2400
2200
2000
1800
1600
1400
1200
1000
800
600 155
28
400
109 207 262
200 433
662
355
525 574 617 711
298 471 754 795
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z-->
- 417 -
PP23
Abundance
Scan 2242 (24.567 min): FSA_199.D (-2249) (-)

59
70000
65000
60000
55000
50000
45000
40000
35000
30000
72
25000
20000
15000 43
10000
5000 86 128
29 114
100 142 184
18 156 170 198
0
10 20 30 40 50 60 70 80 90 100110120130140150160170180190
m/z-->
PP24
Abundance
Scan 2247 (24.611 min): FSA_199.D (-2241) (-)

88
30000
25000
20000
15000
55
10000
29 157
5000
115 297
213 340
186 255 400 429 461 536
364
0
0 50 100 150 200 250 300 350 400 450 500
m/z-->
- 418 -
PP25
Abundance
Scan 2075 (23.105 min): FSA_091.D (-2071) (-)

55000 43
50000
45000
40000
98
35000
30000
25000
20000
267
15000
10000
5000
131
168 210 327364 408 451 491 551 610646 730766
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP26
Abundance
Scan 2340 (25.572 min): FSA_015.D

117
10000
9000
8000
7000 131
6000
5000
41 55 69
4000
3000 101
83
2000
147 203
27
1000 178 239 267 313
160 219 281
295
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
m/z-->
- 419 -
PP27
Abundance
Scan 2364 (25.782 min): FSA_015.D (-2372) (-)

98
450000
400000
43
350000
149
300000 74
250000 239
200000
150000
100000 167
116 257
50000 27
182 299
58
131 213
197 283 315 343 366
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
m/z-->
PP28
Abundance
Scan 2410 (26.185 min): FSA_015.D (-2405) (-)

4000 72
3800
3600
3400
3200
3000
2800
2600
2400
2200 43
2000
1800
1600
1400
1200
1000
114
800
600
155
400 191
223
292327 388
200 428 483 523
253 623
684
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650
m/z-->
- 420 -
PP29
Abundance
Scan 2451 (26.544 min): FSA_015.D (-2456) (-)

2200 98
57
2000
1800
1600
1400
1200
1000
134
253
800
185
600
400 18 313
431
358 520
200 217
469 647 687 739
398 568605 783
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP30
Abundance
Scan 2488 (26.868 min): FSA_015.D (-2483) (-)

98
7500
7000
6500
6000
5500
5000 58
4500
4000
3500
3000
2500
141
2000
1500
1000 237
178 282
500 343
383 429 475 551589 634
16 781
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 421 -
PP31
Abundance
Scan 2500 (26.973 min): FSA_015.D (-2496) (-)

130
6000
5500
5000
4500
4000
3500
3000
2500
2000
191
1500
71
1000
32
237
327
500
490
283 375
426 639 714
548586 750787
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP32
Abundance
Scan 2528 (27.218 min): FSA_015.D

70000 117
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
43
15000
101
10000
75
59 190
5000 133
28 207 341
148 259 281
171
223 241 299 325
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
m/z-->
- 422 -
PP33
Abundance
Scan 2543 (27.349 min): FSA_015.D

98
550000
500000
450000
43
400000
350000
74
300000
134
250000
267
200000
150000
117
100000
154 285
50000 210
27
185 327
169 241
225 311 342359
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
m/z-->
PP34
Abundance

59
450000
400000
350000
300000
250000
200000
150000
100000
97
50000
140
18 184 240 294 337
371 415 461 504540 609647684 749785
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z-->
- 423 -
PP35
Abundance
Scan 2606 (27.901 min): FSA_015.D (-2602) (-)

59
16000
14000
12000
72
10000
8000
6000 43
4000
29 114 128
2000 86 101
147 170 194 209
18 158 182 221 240
251263
0
0 20 40 60 80 100 120 140 160 180 200 220 240
m/z-->
PP36
Abundance
Scan 2614 (27.971 min): FSA_015.D (-2619) (-)

8000 69
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500 207
130 341
1000
500 32 162 254 669

298 387 430 490 595
542 634 718 774
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 424 -
PP37
Abundance
Scan 2631 (28.120 min): FSA_015.D (-2637) (-)

282
8500
8000
7500
7000
6500
6000
5500
5000
4500
70
4000
3500 115
3000
2500
2000
152
1500 28
1000 208
414
500 355
452 501
245 315 561595 639 681 767
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP38
Abundance
Scan 2703 (28.750 min): FSA_015.D (-2699) (-)

98
7000
6500
43
6000
5500
5000
4500
4000
3500 134
3000
2500
2000
295
1500 193
1000
238
500 430
356 477519 583 634
685725 796
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z-->
- 425 -
PP39
Abundance
Scan 2739 (28.919 min): FSA_199.D (-2735) (-)

173
40000
38000
36000
34000
43
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
229
8000
71
6000
4000 341
267
111
2000
201 299 384
141 415 474507 565 660
445 610
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650
m/z-->
PP40
Abundance
Scan 2752 (29.032 min): FSA_199.D (-2747) (-)

59
180000
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000 43
60000
50000
40000
30000 83
20000
126
10000 109
27 154 364
170 191207226 322 348
249267285 305
0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
m/z-->
- 426 -
PP41
Abundance
Scan 2749 (29.153 min): FSA_015.D (-2744) (-)

7000 59
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
112
193
1500
1000 341
429
500 18 149 282
237 623
383 475 524558 686 754
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP42
Abundance
Scan 2796 (29.418 min): FSA_199.D (-2792) (-)

119
22000
20000
18000
16000
14000 91
12000
10000
8000
6000
163
4000
57
2000 207
27
247 281313341
368 401 445 489 550
577 611
0
0 50 100 150 200 250 300 350 400 450 500 550 600
m/z-->
- 427 -
PP43
Abundance
Scan 2847 (29.864 min): FSA_199.D (-2839) (-)

50000 152
45000
40000
35000
30000
25000
20000 70
43
434
15000
10000
123
5000
311
222
190 264 342373
400 505536
462 563597 655
0
50 100 150 200 250 300 350 400 450 500 550 600 650
m/z-->
PP44
Abundance
Scan 2893 (30.267 min): FSA_199.D (-2888) (-)

170
60000
55000
50000
45000
40000
35000
30000 58
124
25000
20000
321
15000
424
10000
209
249
5000
388
27 95 283 459
357 504 550585 623 698
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
- 428 -
PP45
Abundance
Scan 2904 (30.363 min): FSA_199.D (-2898) (-)

170
65000
60000
55000
50000
45000
40000
35000
30000
25000
57
20000
15000 85
219 446
10000 30
5000 131
247 281312341
368 403 475503 549 604 639
0
0 50 100 150 200 250 300 350 400 450 500 550 600
m/z-->
PP46
Abundance
Scan 2732 (28.858 min): FSA_091.D (-2725) (-)

219
9000
8500
8000
7500
7000
57
6500
6000
5500 163
5000
4500
4000
3500
3000
2500 494
2000
129
1500
1000
281
429
500 91
341 549
25 386 461 609 755
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 429 -
PP47
Abundance
Scan 2781 (29.287 min): FSA_091.D (-2774) (-2789) (-)

385
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
280
1500
91 441 590
1000
500 57 159 220

315 475510 551 669708 756
20
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP48
Abundance
Average of 31.666 to 31.718 min.: FSA_015.D - Saturated (-)

441
5000000
4500000
4000000
3500000
3000000
57
2500000
2000000
1500000
147
1000000
308
500000 191
237 646
91
385
15 273 345 503 549589 681 738 786
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
m/z-->
- 430 -
PP49
Abundance
Scan 3173 (32.865 min): FSA_015.D

57
120000
110000
100000
90000
80000
70000
60000
191
50000 647
316
40000 147
30000
20000 91
253
10000
443
355 575
15 401 479 535 611 679 728
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP50
Abundance
Scan 3328 (34.222 min): FSA_015.D (-3317) (-3338) (-)

124
60000
55000
50000
45000
40000
35000
30000
58
25000
20000
321
15000
460
10000 209
167
5000
275 498
15 388 540 598
239 353 427 653689 732
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
- 431 -
PP51
Abundance
Scan 3444 (35.091 min): FSA_199.D (-3453) (-)

7000 119
6500
6000
5500
5000
4500
4000
3500
3000
2500
73
2000
1500
191
1000 267
341
500 27 429
152 236 307 387 490 549 604637671 729
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
PP52
Abundance
Scan 3588 (36.352 min): FSA_199.D (-3577) (-)

284
5500
5000
55
4500
4000
3500
3000
2500
434
2000
115
1500 152
1000
341
500 223
18
185 403 476 517
581 708
624 758
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 432 -
PP53
Abundance
Scan 3605 (36.647 min): FSA_015.D (-3585) (-)

239
2400
2200
2000
1800
1600
74
1400
1200 43 191
1000
313
800 148
105 282
600 503
383
400
447
549 637
200 345 587 671
744
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
PP54
Abundance
Scan 3904 (39.119 min): FSA_199.D (-3883) (-)

57
3000
219
2500
2000
1500
1000
96
147
282
500
185
320 369 638
18 402 491
443 550
583 697735 782
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 433 -
PP55
Abundance
Scan 3960 (39.756 min): FSA_015.D (-3987) (-)

57
4000
3500
98
3000
313
2500
193
2000
239
1500
1000 356
431
148
500 476 551

389
277
591 638 687 727
18 518 786
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 434 -
Overlay of chromatograms (upper, green = PP + additives, red = PP) and EI
spectra (lowest one = PP + additives) of additional peaks observed with GCxGC-
TOF-MS in concentrated ethanol extract of PP + additives.
X1
- 435 -
X2
- 436 -
X3
- 437 -
X4
- 438 -
X5
- 439 -
X6
- 440 -
X7
- 441 -
X8
- 442 -
X9
- 443 -
X10
- 444 -
X11
- 445 -
X12
- 446 -
X13
- 447 -
X14
- 448 -
X15
- 449 -
X16
- 450 -
X17
- 451 -
X18
- 452 -
X19
- 453 -
X20
- 454 -
X21
- 455 -
X22
- 456 -
X23
- 457 -
Mass spectra of the peaks detected in the extracts of the HDPE + additive
samples that were not present in the HDPE samples
HDPE1
Abundance
Average of 6.001 to 6.044 min.: RXN_LSCREEN_060207_023.D (-)

57
34000
32000
30000
28000
26000
24000
22000 145
20000
18000
16000
14000 115
12000
10000
8000
6000
85
4000
2000
166185 207225243261281 313 336356377 405424 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE2
Abundance

57
65000
60000
55000
50000
45000
40000
35000
30000
25000 98
20000
15000
10000
5000
79 124
159 191
208 237 267285306 341 369 394415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 458 -
HDPE3
Abundance

56
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
83
15000
10000
111 182
5000
154
205
130 235 267286 307 339 372 395 417436
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE4
Abundance

55
85000
80000
75000
70000
83
65000
60000
55000
135
50000
45000
40000
35000
30000
25000 111
20000
15000
10000
5000 154 182

205 241259 282 303323342 364 397 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 459 -
HDPE5
Abundance

240000 57
220000
200000
180000
160000
140000
120000
100000 85
80000
60000
40000
20000 112 184

141
165 205 242 265 294 341 372 401 431449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE6
Abundance

30000 43
28000 71
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000 126
96
4000 163
2000
145 194 217
235 281
263 299321343 367387 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 460 -
HDPE7
Abundance

200000 81
190000
57
180000
170000
160000
114
150000
140000
130000
120000
110000
100000
90000
191
80000
70000
60000
50000
40000
30000
20000
163
10000
141
211 233 259 281301319339 387 414 440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE8
Abundance

600000 82
550000
500000
450000
400000 100
350000
300000
57
250000
200000
150000
100000
142
124
50000
167 189 213234 259 281 305 341 376 400 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 461 -
HDPE9
Abundance

86
1300000
1200000
1100000 57
1000000
900000
800000
700000
600000
500000
400000
300000
200000
100000 110 156

128
180198 221 245263281 311 341
358 388 427
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE10
Abundance

72
2800000
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000 43
600000
400000
200000
95
142
124 165 193 221 249 281299 327 355 383 415 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 462 -
HDPE11
Abundance

2800000 58
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000 41
600000
400000
200000 81 140
109
157177 198 220240 265282 309 341 387 412 439
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE12
Abundance

57
4000000
3500000
3000000
2500000
85
2000000
1500000
1000000
500000
113 212
141
169
193 233 263282 307325
343363383 415435
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 463 -
HDPE13
Abundance

191
8000000
7500000
7000000
6500000
6000000
5500000
5000000
4500000 57
4000000
3500000
3000000
163
2500000
2000000 91
115
1500000
1000000 133
500000
209 233 259 282300
318 341 366 401420439
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE14
Abundance

82
700000
650000 43
600000
550000
500000
450000
400000
350000
300000
250000
200000
110
150000
154
100000
50000
180
61 198 220 253 282 309 341 367387 415 436
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 464 -
HDPE15
Abundance

120000 100
110000
100000
90000
80000
70000
60000
50000
40000
30000
57
20000
170
10000 123 152
75 197 223
241259 281 307327
344363 385
403 429
446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE16
Abundance

86
450000
400000
350000
57
300000
250000
200000
150000
100000
50000
110
138156 184
40 206226 252 281 309327 356 385 440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 465 -
HDPE17
Abundance

900000 72
800000
700000
600000
500000
400000
300000
43
200000
100000
95
170
123 152 197 226245263283 307327 355 385404 435
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
HDPE18
Abundance

1100000
58
1000000
900000
800000
700000
600000
500000
400000
300000
200000
100000 81 168
109
127 151 191 226
209 259 283 307325 355 387 417 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 466 -
HDPE19
Abundance

57
5500000
5000000
4500000
4000000
3500000 85
3000000
2500000
2000000
1500000
1000000
113
500000 240
141
169
197
219 259 283 313 341 380 402420438
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE20
Abundance

360000 57
340000
320000 82
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
110
60000
40000
138 182
20000
208
160 238259 281 304 327 356 383 415 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 467 -
HDPE21
Abundance

70000 55
65000
60000
55000
50000
45000
40000
35000 88
191
30000
25000
20000 166
209
15000 124
10000
254
5000 147 281 415
341
106 230 311 367385 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE22
Abundance

86
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000
20000 56
10000
152173193 224 254
113 272290 321 355 384 408429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 468 -
HDPE23
Abundance

88
65000
60000
55000
50000
45000
40000
35000
149
30000 41
25000
69
20000
15000 213
10000 111 270

5000 241
129 185
167 415
289309 341 369387 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE24
Abundance

600000 86
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
56
50000
254
149
112131 183201 224 281299317 341 372392 415 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 469 -
HDPE25
Abundance

100
170000
43
160000
150000
140000
130000
120000
110000
100000
90000
71
80000
70000
60000
50000
124
40000
30000
194
20000
152
10000
211 268
170 236
289 314 341 363 396 420 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE26
Abundance

2400000
277
2200000
2000000
1800000
1600000
1400000
1200000
1000000
57
800000
147
600000
219
400000
200000 91 128 185

253
109 166 295 327 355 385 415 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 470 -
HDPE27
Abundance

174
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000
59
120000
100000
80000
60000
130
40000 41 328
20000
98 156 198 224
77 242261280
298 356 389408429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE28
Abundance

88
280000
260000
240000
220000
200000
180000
160000
140000
120000
57
100000
80000
298
60000 157
255
40000
111 213
20000
129
185 235
278 319 341 401
359 383 419 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 471 -
HDPE29
Abundance

55
160000
150000
140000
130000
120000
110000
83
100000
174
90000
80000 250
70000
60000 208
50000 110
40000
30000 155
137
296
20000
10000 401
232 328
268 355 429448
373
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE30
Abundance

174
500000
450000
400000
350000
300000
250000
200000
55
150000
98
100000
130 208
253
50000 151 328
79
228 284 309 357 380 403 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 472 -
HDPE31
Abundance

240000 116
220000
59
200000
180000
160000
140000
120000
100000
80000
60000
40000 86
20000 198
256
143 170 217235 277 308329 355 390 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE32
Abundance

43 211
650000 98
600000
118
550000
500000
450000
400000
74 242
350000
300000
250000
200000
143
150000
100000
185
50000
167
271 296317 339357 390 416 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 473 -
HDPE33
Abundance

174
800000
750000
700000
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
211
150000
130 254
100000
60 328
50000
229
89 280300
156 193 346 371392 417438
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE34
Abundance

174
160000
150000
140000
130000
59
120000
110000
100000
90000
80000
70000
60000
115
50000
40000 136
97
30000
20000 328
41 220
79
10000 192
281
155 248 300 357 415
386 442
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 474 -
HDPE35
Abundance

900000 118
800000
700000
600000
500000
400000
300000
200000 256
88
100000 55 136
164 192 220
278 311 343 371 401 429
446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE36
Abundance

55
340000
83
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000 111
120000
100000
80000
60000 136
40000
20000 213 263

164 192 234
281299 329 355 386 415 446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 475 -
HDPE37
Abundance

1800000
174
1600000
1400000
1200000
1000000
800000
600000
400000
130
200000 328
41 59 89 108 156 200 224 256 284306 346 371389 414 442
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE38
Abundance

174
6000000
5500000
5000000
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000 130
328
500000 43
88
69 281
112 155 200 224242262 300 346 371389 415 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 476 -
HDPE39
Abundance

118
3500000
3000000
2500000
2000000
256
1500000
1000000
74
43
500000
97 154 184 224 286 308327

136 356 384 414 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE40
Abundance

55
380000
360000
340000 83
320000
300000
280000
260000
240000
220000
200000
180000
160000 111 281
140000
120000
100000
80000
60000
137
40000
155 222
180
20000
199 246 310
343363381402 429446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 477 -
HDPE41 (co-eluting)
Abundance

59
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
81 126
253
200000
100 281
41 154 210
174192 235 310328346366384
402 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE41 (co-eluting)
Abundance

256
6000000
74
5500000
118
5000000
4500000
4000000
3500000
3000000
43
2500000
2000000
1500000
284
1000000
185
224
500000
98 154
206 319 342360 382 415 440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 478 -
HDPE42
Abundance

2200000 59
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
41
200000 86 128 212
170 255
104 191 232 281 312 337355374 401 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE43
Abundance

8000000 57 85
7500000
7000000
6500000
6000000
5500000
5000000
4500000 113
4000000
3500000
3000000
141
2500000 310
2000000
169
1500000
197
225 253
1000000
500000 281
328 355 386405 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 479 -
HDPE44
Abundance

55 97
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000 125
308
6000
4000
281
153 342 415
2000 182 208
75 248 387
368 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE45
Abundance

118
1800000
1600000
1400000
1200000
256
1000000
800000
600000
400000
74
200000
56
100 140160 182200 224 286 310330 355 390 415436
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 480 -
HDPE46
Abundance

174
1500000
1400000
1300000
1200000
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
328
200000 118
100000
43 256
75 224
100 146
200 276 298 356 382402 429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE47
Abundance

55
800000
750000
700000
650000
600000
98
550000
500000
450000 236
400000
350000
300000
250000
179
200000 137
150000
79
100000 272
207
50000
155 312
119 294 334 357 382401 430449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 481 -
HDPE48
Abundance

90000 237
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000 72
25000
20000
15000
116
10000
5000
188 263281300
50 160 322 344 370 402 430448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE49
Abundance

256
7000000
6500000
6000000
88
5500000
5000000
4500000
4000000
3500000
3000000 118
2500000
2000000 43
1500000
1000000
500000 69 212
140 168 286
186 230 309330 357 384
402 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 482 -
HDPE50
Abundance

256
1300000
1200000
1100000
98
1000000
900000
800000
58
700000
600000
500000
400000
300000
131
200000
227
100000 154
185
79
209
275 299 324 356 382402421 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE51
Abundance

181
650000
600000
256
550000
500000
450000
400000
350000
300000
250000
200000 116
91
150000
100000
50000 41
65 152
202 226 274
134 295313333 356 382 404422443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 483 -
HDPE52
Abundance

1100000 174
1000000
900000
800000
700000
600000
500000
400000
118
300000
55
200000
250 356
81
100000 284
137
100 207 326
155 232 307 374395 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE53
Abundance

59
4000000
3500000
3000000
2500000
2000000
41
1500000
1000000
83 126
500000 281
154 238
101 184 207 309
263 341 369387 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 484 -
HDPE54
Abundance

8000000 59
7500000
7000000
6500000
6000000
5500000
5000000
41
4500000
4000000
3500000
3000000
2500000 126
2000000 81
281
1500000 100 256
1000000 154
238
184
500000
220 309
202 340359380
398 430449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE55
Abundance

57
5500000
5000000
4500000 85
4000000
118
3500000
3000000
284
2500000
2000000
1500000
1000000
141
169 338
500000
197
225 253
309
356376 404 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 485 -
HDPE56
Abundance

55
5000000
4500000
264
98
4000000
3500000
3000000
2500000
2000000
1500000
137
1000000 79
221
165
500000
119 193 340
246
296 322
371 396 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE57
Abundance

118
400000
350000
300000
250000
200000 284
150000
100000 74
50000
44 154 210 255
100 187 229 314 336354 382401 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 486 -
HDPE58
Abundance

129
105000
100000
95000
90000
85000
80000
75000
70000
256
65000
60000
55000 284
50000
45000
40000
35000
30000
25000
185
20000
88
15000
10000 337
57 239
155
5000 312 371
203
106 398 431
449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE59
Abundance

256
1800000
1600000
1400000
1200000
1000000
300
800000
600000
400000 88
162
200000 45
132
70 112 182 224 330
200 274 361 384404423
441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 487 -
HDPE60
Abundance

2000000 284
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000
57 88 118
196216 252 314 340
139 161 234 358 382404 430
448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE61
Abundance

57
280000
260000
240000
220000
200000
180000
85
160000
140000
120000 337
100000
80000
60000
40000 113
141 308
20000 169 210
238
189 261280 371 395415
432
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 488 -
HDPE62
Abundance

96
75000
70000
65000 55
60000
55000
50000
45000
40000
35000
30000
25000
362
20000
123
300
15000
10000
222
152
194
5000
250272 343
74 170 325 386 408429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE63
Abundance

600000 131
550000
500000
450000
400000
350000
300000
250000
55
200000
150000 101
100000 83
203 264 412

50000 236
292
151
179 316 341 369 392 430447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 489 -
HDPE64
Abundance

3200000 55
264
3000000
2800000
2600000
98
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
137
800000
79
600000
221
166
400000
325
200000 119 193
246 307
285 356
382 412431449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE65
Abundance

368
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000 105
16000 43
14000
12000
255
10000 71
159 314
8000
213
131
6000
4000 393
282
2000 185
234 339 411
440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 490 -
HDPE66
Abundance

368
300000
280000
260000
240000
220000
200000
180000
160000
140000 147
120000 105
81
43
100000
80000
247
60000 213
40000 129
20000 171
326
191 283
63 301 350 393 415 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE67
Abundance

80000 282 329
254
75000
70000
65000
60000
55000
57
50000
45000
40000
35000
30000
441
25000
147
20000
15000
10000
91
5000 119 191
168 219
310 356 379399417
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 491 -
HDPE68
Abundance

95000 254
90000
282
85000
80000
75000
70000
65000
60000
55000
50000
45000
347
40000
35000
30000
25000
20000
15000
10000
427
91 147
5000 191
40 117 219 300
168 327 396
72 371 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE69
Abundance

385
110000
100000
90000
441
80000
70000
57
60000
50000
40000
30000 91 147
280
20000
10000
117 191 237
165 219 329
257 310 355 410
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 492 -
HDPE70
Abundance

42000 385
40000
38000
36000
34000
32000
30000
28000
57
26000 201
24000
22000
20000
18000
127
16000
14000
12000 147
10000
441
8000 265
6000 81
4000 109 339
2000 219 295

175 241 313 417
367
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE71
Abundance

120000 57
110000
100000
90000
80000
70000
60000
449
50000 85
40000
30000
20000
113
10000 141 282
169 207 253 326 421
187 225 308 344365 399
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 493 -
HDPE72
Abundance

120000 328
110000
100000
90000
80000
70000
60000
50000
40000 256
30000
20000
43
10000 88
69 160 238
118 142 212 298
183 279 348369 398 426 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE73
Abundance

105000 256
100000
95000
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000 43
328
20000
15000 238
88
10000
69
298 356
5000 140 212
118 169
191 380
398 433
276
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 494 -
HDPE74
Abundance

57
4000000 219
3500000
3000000
2500000
2000000
1500000
147
278
1000000
83 189
500000
167
107 129
247 317 345 374 402 431
297 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE75
Abundance

356
800000
700000
600000
500000
400000
300000
200000 283
256
100000 43
88 160 328
70 118 142 183 212 238 301 384 412 440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 495 -
HDPE76
Abundance

130000 389
120000
110000
100000
333
90000
80000
57
70000
60000
50000
40000
30000 282
20000
183
147 427
91
10000 117
165 201 235 259 315 359
407 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE77
Abundance

57 382
60000
55000
50000
45000
40000
35000
85
30000
25000
20000
15000
256
10000 309
111
356
5000 155 238
183 211 281
131 337 416 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 496 -
HDPE78
Abundance

71
9500
9000
8500
8000
7500
356
7000
6500
6000
5500
5000
4500
4000
3500
3000 97
2500
2000
1500 308
250 416
117 208
1000 163
278 336
500 135 435
182 230 375 399
46
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE79
Abundance

256
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000 43 283 356
60000
238
88
40000
20000 70
212
126 168 328
107 147 186 307 374394412 440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 497 -
HDPE80
Abundance

389
1100000
1000000
900000
800000
700000
600000
500000
333
400000
57
300000
200000
183
100000
282 427
91 147
117 201 356
165 235 259 315 407 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 498 -
Mass spectra of the peaks detected in the extracts of the PS + additive samples
that were not present in the PS samples
PS1
Abundance
Scan 415 (8.568 min): FSA_203.D (-405) (-)

57
7000
6500
6000
5500
5000
4500
4000
3500 41
3000
2500
2000
1500 29
70
1000 83
500 98
17 51 65 91 106 112
78
0
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100105110
m/z-->
PS2
Abundance
Scan 952 (13.270 min): FSA_203.D (-946) (-)

104
3000
76
2500
2000
1500
50
1000
500
148
17 194 237 432 580
0
0 50 100 150 200 250 300 350 400 450 500 550
m/z-->
PS3
- 499 -
Abundance
Scan 1225 (15.660 min): FSA_203.D (-1220) (-)

57
8000
7000
6000
5000
71
43
4000
3000
2000
29
112
1000 83
98
15 131143 207 232 250 281
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280
m/z-->
PS4
Abundance
Scan 1251 (15.888 min): FSA_203.D (-1246) (-)

175
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
115
2000
1500 77
41
1000
500
222 316355 774
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 500 -
PS5
Abundance
Scan 1488 (17.963 min): FSA_203.D (-1482) (-)

121
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000 163
6000
41
4000
91
2000
220
401 699
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
m/z-->
PS6
Abundance
Scan 1503 (18.094 min): FSA_203.D (-1494) (-)

135
25000
20000
15000
10000
5000
107
28 95 119
16 44 60 76 161
173 193206220 281
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280
m/z-->
- 501 -
PS7
Abundance
Scan 1512 (18.173 min): FSA_203.D (-1507) (-)

60000 135
55000
107
50000
45000 149
40000
35000
30000 121
25000
20000
15000 41 55
10000 77 91 191
29
5000 220
17 161175 208 235 282295
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280
m/z-->
PS8
Abundance
Scan 1523 (18.269 min): FSA_203.D (-1519) (-)

85000 135
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
41
10000
91
5000
180 220
267 403 745784
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 502 -
PS9
Abundance
Scan 1537 (18.392 min): FSA_203.D (-1533) (-)

135
24000
22000
121
107
20000
18000
16000
14000
12000
10000
163
8000
6000 41
4000 77 91 177
2000 27 55
220
197 237 278 296 316
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
m/z-->
PS10
Abundance
Scan 1548 (18.488 min): FSA_203.D (-1544) (-)

107
35000
149
30000
25000
20000
15000
10000 177
55
5000
29
79
220 252 385 417 575
0
50 100 150 200 250 300 350 400 450 500 550
m/z-->
- 503 -
PS11
Abundance
Scan 1561 (18.602 min): FSA_203.D (-1563) (-)

135
110000
100000
90000
80000
70000
60000
50000
40000
30000
107
20000
41
10000
16 65 84 162 194 220 248 281 322341 411

0
20 40 60 80 100120140160180200220240260280300320340360380400
m/z-->
PS12
Abundance
Scan 1574 (18.716 min): FSA_203.D (-1580) (-)

26000 135
25000
24000
23000
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000 41
3000
2000 91
1000 220
178
265302 358 453 767
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 504 -
PS13
Abundance
Scan 1612 (19.048 min): FSA_203.D (-1603) (-)

135
12000
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500 107
2000
1500 41
1000
77
500
234
17 155175 209 261283 447
0
50 100 150 200 250 300 350 400 450
m/z-->
PS14
Abundance
Scan 1676 (19.609 min): FSA_203.D (-1672) (-)

7000 161
6000
5000
4000
135
3000
235
2000
91
41
1000
190
15 281 602
0
0 50 100 150 200 250 300 350 400 450 500 550 600
m/z-->
- 505 -
PS15
Abundance
Scan 1751 (20.265 min): FSA_203.D (-1749) (-)

161
3200
3000
2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
28 57 249
600 105
400 128
200 190
81
221 281 489 550
0
0 50 100 150 200 250 300 350 400 450 500 550
m/z-->
PS16
Abundance

1200000 225
1100000
1000000
900000
800000
700000
600000
500000
93
400000
300000
168
200000
51
100000
127
15 258297 354 404 447 571 613 663 725 776
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 506 -
PS17
Abundance
Scan 1788 (20.589 min): FSA_218.D (-1779) (-)

35000 135 223
30000 45
25000
20000
15000
10000
107
5000 77
161 294
19 192 263 323 595
0
0 50 100 150 200 250 300 350 400 450 500 550 600
m/z-->
PS18
Abundance
Scan 2104 (23.356 min): FSA_203.D (-2100) (-)

185
36000
34000
43
32000
30000
129
28000
26000
24000
22000
20000
18000
16000
14000
12000
259
10000
8000
157
6000
111
4000
87 213
2000 61
26 329
233 276 306 374
0
0 20 40 60 80 100120140160180200220240260280300320340360380400
m/z-->
- 507 -
PS19
Abundance
Scan 2334 (25.370 min): FSA_203.D (-2326) (-)

60000 149
55000
50000
45000
40000
35000
30000
57
25000
20000
15000
10000
113
5000 29
84 279
210233257
189 339362387
318 426 505
0
0 50 100 150 200 250 300 350 400 450 500
m/z-->
PS20
Abundance
Average of 25.746 to 25.895 min.: FSA_203.D - Saturated (-)

149
5000000
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
57
500000 279
113
207
15 245 333 391429 473 535 607 697732 780

0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 508 -
PS21
Abundance

80000 161
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
57
20000
15000
10000
217 368
121
5000 263
312 530 586

19 415 474 619652
685 725 785
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 509 -
Mass spectra of the peaks detected in the extracts of the PET + additive samples
that were not present in the PET samples
PET1
Abundance
Scan 2433 (26.237 min): FSA_197.D (-2425) (-)

119
6500
6000
5500
5000
4500
4000
3500
3000
2500 91
2000
28
55
1500
189
218246
1000 161
500
283311 341 565

0
0 50 100 150 200 250 300 350 400 450 500 550
m/z-->
PET2
Abundance

48000 91
46000
44000
42000
40000
38000
432
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000 41
12000
165 342
10000
8000
128
6000
4000
252
2000 209
284
388 475 516 563 609647 689 759
0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
m/z-->
- 510 -
Mass spectra of the peaks detected in the extracts of the PVC + additive samples
that were not present in the PVC samples
PVC1
Abundance

700000 47
650000
600000
550000
500000
450000
120
400000
350000 74
300000
250000
200000
150000
100000 92
50000
145163 189 221 249 284305325

266 343 369
386 416 446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC2
Abundance

19000 161
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
105
8000
7000
6000
5000 77
4000
133
3000
2000 59
40
1000 209
268 295 342 415
191 238 313 367385 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 511 -
PVC3
Abundance

43
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000
68
1000 193
99 129
147165 219 241259 281 315 341 366 401 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC4
Abundance

260000 57
240000
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000
20000 99
40 79 133 155
116 172192
208 230 259 282 307327344 383401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 512 -
PVC5
Abundance

83
30000
28000
26000
24000
22000
20000
18000
43
16000
14000
12000
129
10000
8000
6000
4000 111
2000
60 159 185203 229 259
276295 327 355 404 434
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
PVC6
Abundance

81
52000
50000
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
138
10000
53
8000
6000
4000
2000 109
159 181 207 234 257 283301 327 355 378 418 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 513 -
PVC7
Abundance

41
18000
17000
16000
15000
14000
13000
12000
11000
84
10000
9000
8000
7000
6000
5000
4000
3000
120
2000
1000 66
101 152170 193 219238 259 281300 326 356 387 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC8
Abundance

7000000 57
6500000
6000000
5500000
5000000 83
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000 112
500000
130 165185 207 229 259281 313 341 364383402 431449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 514 -
PVC9
Abundance

57
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000 83
80000
60000
40000
20000 112
134 161179 207 234 259 282 309 334355374 403 430448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC10
Abundance

113
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
85
59
6000
4000
40
2000
143
165185 208226243 267 291 316 342 365 389 412430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 515 -
PVC11
Abundance

75000 57
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
83
15000
10000
113
5000
141
158 185 215
232
249 281299 323 356 400 431
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
PVC12
Abundance

34000 57
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
98
8000
6000
4000
2000
79 124 185 209 234 341362 385
148167 252 281 309 414 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 516 -
PVC13
Abundance

11000 207
10500
10000
9500
9000
117
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
43
3500
3000
237
2500
2000 89
1500 179 281
1000 145
61
500 327 415
255 356 385 445
299
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC14
Abundance

56
16000
15000
14000
13000
12000
11000
10000
83
9000
8000
146
7000
6000
5000
4000
3000 112
2000
355
1000 207
185 267
129 168 237 296 327 385 408429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 517 -
PVC15
Abundance

1100000 43
1000000
70
900000
800000
700000
600000
500000
400000
300000
200000
112
100000
91 139157 185 209 236 262281 305323

341 369 398417 439
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC16
Abundance

170000 43
160000
150000
140000
130000
120000
110000
100000
90000
80000 120
70000
60000
50000
40000
30000
89
20000 162
10000
61
141 194 222 249267 295313 341 371 401 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 518 -
PVC17
Abundance

99
7500000
7000000
6500000
6000000
5500000
5000000
127
4500000
4000000
3500000
3000000
2500000
2000000
54
1500000
1000000
500000 72
145
172 207 229 259281 305325
343 369 401 430448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC18
Abundance

57
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000
118 147
2000
89 207
167185 232 259 283 309329 356 385405 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 519 -
PVC19
Abundance

280000 127
260000
240000
220000
200000
180000
160000 99
140000
120000
100000
80000
60000 55
40000
20000 81
145
173193 219240259 281 309 333
351
369 401 431
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC20
Abundance

41
6000
5500 69
5000
4500
4000
3500
3000
97
2500
2000
1500
168
1000
500 140
119
187207 267
235 284304 327 357 382 415
432
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 520 -
PVC21
Abundance

267
6500
6000
5500
5000
4500
4000
3500 341
3000
2500
2000 285
1500 311
1000 56 82 193
237
141 401
112
500
163 429
211 369
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC22
Abundance

40000 88
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
57 127
14000
12000
10000
8000
6000
4000
2000
109 151172 282
207 237 265 304325 356 401
383 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 521 -
PVC23
Abundance

46000 57
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000 85
12000
10000
8000
113
6000
4000 170
2000 141
193211229 259 283300 327 355 387406 427447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC24
Abundance

8500 43
8000
7500
7000
6500
6000
5500
5000
70
4500
4000
3500
3000
2500 112
2000
95
1500
1000
500 138 259 281

156 187208 233 307327 348369 395 431
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 522 -
PVC25
Abundance

217
4500
105
4000
133
3500
3000
2500
2000
45
75
1500
1000
500 265
195 325 402
161
235
284 344 373 430
306
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC26
Abundance

6000 133
5500
5000
4500
4000
3500
3000 59
103 163
2500 250
2000 41
1500
269
208
1000
77
357
500
181 402
311 339 429
230 293 383 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 523 -
PVC27
Abundance

57
5000
125
4500
4000
3500
3000
2500
2000
84
1500
1000 415
327
185 207
500
105
40 166
148 267
235 284 307 355 383
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
PVC28
Abundance

61 88
10000
9500
9000
8500
8000
7500 115
7000 176
6500
6000 43
5500
5000
4500
4000 341
3500
133
3000
2500
2000
1500
385
1000
207 281
500 237
156 311 403 429
255 359 446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 524 -
PVC29
Abundance

99
38000
36000 43
34000
32000
30000
28000
26000
24000
22000
20000
18000
74
16000
14000
12000
10000
8000
6000
117
4000
157
2000
138 191209 235 259 283 309 341 380397415432
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
PVC30
Abundance

17000 117
16000
15000 71
14000
13000
12000
11000
10000 89
9000
8000
7000
6000
5000 53
4000
3000
2000
145
1000
174 208 267
191 235 297315 341359 386
402 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 525 -
PVC31
Abundance

85
18000
17000
16000
15000
14000
43
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000 104
135155 191
62 173 209 235 268 295313331 362382401 430
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
PVC32
Abundance

57
65000
60000
55000
50000
45000
40000 101
75
35000
41
30000
25000
20000
15000
10000 150
124
186
5000
169 209 238 262280 313 341 376395414

0
40 60 80 100120140160180200220240260280300320340360380400
m/z-->
- 526 -
PVC33
Abundance

281
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
103
3500
3000
2500
355
2000 73
43 191
1500
149 251
1000
221 325
500 131 385
403 431
172
301
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC34
Abundance

43
20000
19000 69
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
87
7000
129
6000
5000
4000
3000
2000
105 159
1000 193
221 251 282301321341
358 382 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 527 -
PVC35
Abundance

57
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000 85
18000
16000
14000
12000
10000
8000
6000
4000 184
112
2000 141
165 207 236 259 281301 327 357 401 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC36
Abundance

70
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000 41
7000
6000
5000
4000 91 112
3000
149
2000
1000 130
167 191 217235 259 281 327
309 355373393411429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 528 -
PVC37
Abundance

320000 57
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000 83
60000
40000 112
20000
157
139 185 209 230 259 281 306324341 370 402 425443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC38
Abundance

5000 89
4500
4000
3500
3000
2500
147
2000 40
114
1500
1000
500
60
167 189207 341
281
228 249 303 377 401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 529 -
PVC39
Abundance

145
170000
160000
150000
140000 103
130000
120000
110000
100000
90000
80000 71
70000
60000
50000
40000
30000
45 128 174
20000
10000
87 190207 237 267283 311329 356 378 415

0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400
m/z-->
PVC40
Abundance

120
8000
7500
7000
6500
6000
43
5500
5000
73
4500
190
4000
3500
3000
101
2500
2000 144
1500
1000 415
356
500 237 281 328 387
162 210 255 308 439
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 530 -
PVC41
Abundance

100000 99
95000
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
127
30000
25000
20000
15000 47
10000 145
82
5000
64 162 190209 233 259 281 303 325342 364 395416

0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
PVC42
Abundance

400000 57
380000
360000
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
83
140000
120000
100000
80000
60000
112
40000
20000
139157177 208 234 259 281 309329348 377 401421 448

0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 531 -
PVC43
Abundance

133
65000
60000
55000
203
50000
45000
40000
35000
156
30000
177
25000
75
20000
15000 109
248
10000 45
5000
230 281299 328 355 387 417 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC44
Abundance

18000 127
17000
16000
145
15000
14000
13000
12000
11000
10000
56
9000 99
8000
7000
6000
5000
4000
3000
81 245
2000
1000 415
175 282 355
210 264 311329 385 433
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 532 -
PVC45
Abundance

36000 43
34000
32000
30000
28000
26000
24000
115
22000
20000
18000
16000
14000
143
12000
71
10000
8000
6000
4000 89
2000
163 196215233 267285 309 340 379 415 448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC46
Abundance

41
20000
19000
18000
17000
16000
83
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000 111
4000
3000
2000
1000 143 168

196
64 215 249267286 321341360 381 415
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 533 -
PVC47
Abundance

113
220000
200000
180000
160000
140000
120000
86
100000 141
80000
60000 41
40000
68
20000 159
193214233253 283 309 341 369387 417 446

0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC48
Abundance

36000 160
34000
32000
30000
28000
26000
24000
22000 105
77
20000 133
18000
16000
14000 206
45
12000
10000
8000
6000
4000
2000 267
341
178 238 299 323 369 405 429
387 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 534 -
PVC49
Abundance

43
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000 120
71
16000
14000
12000
10000
190
8000 144
6000
4000
102
2000
163 208 233251 281 313 342 371 401 430449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC50
Abundance

21000 191
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
105
8000
7000 57
6000
5000
4000
3000 131
87 163
2000
1000 237 341 415

387
217 268 295 323 369 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 535 -
PVC51
Abundance

71
5000000
43
4500000
4000000
3500000
3000000 112
2500000
2000000
1500000
1000000 92
145
500000
175 204 229247267285 311 341362381401 429449

0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC52
Abundance

205
8000000
7500000
7000000
6500000
6000000
5500000
5000000
4500000
4000000 57
145
3500000
3000000
177
2500000
105
2000000
81
1500000
1000000
500000 127
223
241259281 307 341360 387 415 437
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 536 -
PVC53
Abundance

57
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
85
8000
7000
6000
5000 197
4000
112
3000 149
2000 251 281

131 223
1000 177 416
327 352
307 383 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC54
Abundance

60
5000
4500
4000
3500
3000
41 251
2500 207
2000
99 341
1500
137
1000
79 177
117
500 159 389

225 365
269 309 445
418
289
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 537 -
PVC55
Abundance

57
600000
550000
500000
450000
400000
350000
300000
85
250000
200000
112
150000
140
100000
50000
211
168
194 234251 281 327
310 354 382401 429
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
PVC56
Abundance

57
190000 101
180000
170000
160000
129
150000
140000
130000
120000 83
110000
100000
90000
80000
199
70000
60000
50000
40000 157
30000
224
20000
10000 175
252 281 309327 355 388 415 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 538 -
PVC57
Abundance

83
36000
34000 112
32000
30000
28000
26000
24000
22000
20000
224
18000
16000
14000
12000
190
10000
8000
6000
65
4000
2000 135
47 162
249268289309 341360 382 415435
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC58
Abundance

119
30000
28000
26000
43
24000
22000
20000
18000
16000
14000 190
12000 91
10000
8000
6000
65
4000
2000 159
138 224 254275295 327 355 388
405 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 539 -
PVC59
Abundance

32000
43
30000
28000 155
26000 117
24000
22000
20000
18000
16000
99
14000
12000
173
10000
8000
73
6000
207
4000 341
2000
137
225 254 281 309 369
387
417 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC60
Abundance

5500000 113
5000000
4500000
4000000
3500000
3000000
2500000
2000000 86
57
1500000
1000000
131
169
500000
187
150 213 242262281 309327 355 387 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 540 -
PVC61
Abundance

240000 43 71
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000 99
226
20000 127
154 183 207 341
251 281 313 387
369 405 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC62
Abundance

7000000 57
6500000
6000000
5500000
5000000
4500000
4000000 85
3500000
3000000
2500000
113
2000000
1500000
1000000
226
500000 141 169
197 259 281 309 341 363 385 415 439
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 541 -
PVC63
Abundance

217
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000 57
112
5000 157 189
91 139
253 275
235 293 323 355 385404 430
448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC64
Abundance

75000
112
70000
65000
60000
55000
50000 139
45000 212
40000
35000
30000 84 167
25000
20000
185
15000
10000 43
5000
66
239258 285 309 342 367385
402 430449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 542 -
PVC65
Abundance

36000 59
34000
32000
30000
28000 192
26000
24000
22000
20000 119
238
18000
165
16000
14000
12000
10000
8000
79
6000
4000
2000
41 97 282 388
137 215 263 328
310 356 416 444
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC66
Abundance

112
260000
240000
220000
200000
180000
160000
140000
120000
169
100000
80000
57
60000
131
40000 85
187
20000
149 205224242261281 309328 355 383401 429447

0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 543 -
PVC67
Abundance

157
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
115
30000
25000
20000
43 203
15000
10000
301
69 87
5000 139
185 265 325 355
238 284 373392 415433
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC68
Abundance

8000000 71
7500000
7000000
6500000
43
6000000
5500000
5000000
4500000
4000000
3500000
3000000
112
2500000
2000000
1500000
1000000
500000 131
157 185
89 203222242 267
285 309 341360381401419 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 544 -
PVC69
Abundance

45
6000
5500
5000
4500
4000
3500
163
205
3000
334
2500 89 133
2000
1500
267
1000 415
355
500 249 388
445
295
65 186
225 315
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC70
Abundance

90 172
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000 43
65 137
140000
120000
100000
80000
60000
40000 112
228
20000
204
249 283 309329351 383 415 444
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 545 -
PVC71
Abundance

43
18000
17000
126
16000
15000
14000 81
13000
12000
11000
10000
9000
8000
154
7000
6000
5000
210
4000
3000
238
2000 191 387
61 108 341 415
1000 445
311
269 293 367
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC72
Abundance

43
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000
20000 126 154

73 183 207 341
105 256 281301 323
238 367387 418 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 546 -
PVC73
Abundance

155 173
38000
36000
34000
32000
30000
28000 56
26000
91
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000 225
2000 135
196 281
113 251 310328 355 385 416436
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC74
Abundance

105
36000
34000
32000
30000
28000
26000
24000
22000
20000
70
18000
16000
14000
12000
10000
8000
123
6000
4000
2000 225
163 184 267
142 242 284 309 341
49 88 202 358 381401 422 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 547 -
PVC75
Abundance

91
900000
800000 173
700000
155
600000
500000
56
400000
300000
200000
100000
203
115 228 250 273293
74 133 311329 355 384
401 430
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC76
Abundance

91
750000
173
700000
650000
600000
155
550000
500000
450000
400000
56
350000
300000
250000
200000
150000
100000
50000
109 228
134 203 246 273 307327 355 381401 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 548 -
PVC77
Abundance

40000 103
38000
36000
34000
32000
30000
28000
43
26000
24000
22000
20000
18000
16000
159
14000 229
211
12000
10000 75 140
8000
260
6000 183
4000
2000 343 387 415

122 281 313 369 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC78
Abundance

43
700000
145
650000
600000
550000
500000
450000
400000
89
350000
300000
250000
200000
150000 71
100000
215
50000 117
187 246
166 268 289309 342361 382 415433
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 549 -
PVC79
Abundance

88
75000
70000
65000
60000
55000 149
207
50000
45000 57
40000
35000
30000
25000 131
279
20000
249
15000
10000 225
408
5000 112 167185
298 326 356 385 427445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC80
Abundance

112
700000
650000
600000
550000
500000
185
139
450000
400000
350000
300000
250000
200000 212
84
150000 41 157
100000 241
50000
66
266286307327 355 388 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 550 -
PVC81
Abundance

112
300000
280000
260000
240000
220000 185
200000 139
180000
160000
140000
120000
100000
212
80000 84
157
41
60000
241
40000
20000
66
286
268 313 343 369 399 429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC82
Abundance

172
128
800000
750000
700000
650000
600000
550000
500000
450000 73
400000 219 246
350000
300000 100
55
250000
200000
150000 292
100000
147 200
50000
267 355
313 337 381402 430
448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 551 -
PVC83
Abundance

57
75000
70000
65000
60000
55000
50000
45000
85
40000
35000
30000
25000
20000
15000
10000 127
155 268
5000
182 211
107 239 289307327 355374394415 446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC84
Abundance

157
4000000
3500000
3000000
2500000
2000000 203
1500000
43
1000000
115
185
500000
139
245
85 301
67 273
227 327 355 388 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 552 -
PVC85
Abundance

57
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
160
15000
132
10000 83 190
103
274
5000 217
253
235 292311 343 365383 416
433
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC86
Abundance

157
4000000
3500000
3000000
2500000
2000000 203
1500000
43
1000000
115
185
500000
139
245
85 301
67 273
227 327 355 388 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 553 -
PVC87
Abundance

88
450000
400000
350000
300000
250000
200000
43
150000
100000 70 157 284

241
50000
115 213
185
139
259 311 341
358 385403 429
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC88
Abundance

157
750000
700000
650000
600000 185
231
550000
500000
450000
400000
43
350000
300000
250000
129
200000
150000
100000
111
301
50000
87 273
69 213 329
249 355373 401 429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 554 -
PVC89
Abundance

2400000 112
156
2200000
2000000
1800000
1600000
1400000
138
1200000
1000000
800000
600000
212
400000 42 71
200000
94 184 239257 281 310

328 355 383401 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC90
Abundance

41 129 185 259
8000000
7500000
7000000
6500000 157
6000000
5500000
5000000
4500000
4000000
111 329
213
3500000
3000000
2500000
2000000
1500000 84
1000000 61
500000 301 403
241 361
281 383 429
447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 555 -
PVC91
Abundance

200000 145
190000
180000 116
170000
160000
150000
98
140000
201
130000
173
120000
110000
100000
90000
80000
70000
242 316
60000
289
50000
73
40000
362
30000
20000 55
269
10000
219
335 384 413 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC92
Abundance

343
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
315
4000
3500
3000
2500
2000 40
221
1500 431
169 287
94 192
266
1000
240 389
500 62 122 371
413 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 556 -
PVC93
Abundance

166
6000
5500
138
5000
4500
199
4000
3500
40
3000
2500
95 295
2000 221240
271
1500
1000 369
323
62 118
500 347 432
400
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC94
Abundance

60000 112 157
55000
50000
45000
241
40000
55
139
35000
30000
25000
185
20000
315
15000 213
10000 84 269
5000
297
341 371 396416 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 557 -
PVC95
Abundance

85000 55
80000
75000
70000
65000 81
60000
55000
50000
45000
40000
35000
30000 99
25000
121
20000
164
15000
10000 139
207 279
303
247
5000
189
229 322341361 386 416 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC96
Abundance

112
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000 259
14000
12000 303
10000 212
174
8000
6000 87
152 231
4000 63 277
2000 329
361 406
40 134 386 430448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 558 -
PVC97
Abundance

155
55
4500000
4000000
88
3500000
3000000
2500000
2000000
109
1500000
1000000 185
213
136
500000
263281
245
308326 355 387 415 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC98
Abundance

280000 56
260000
285
240000
220000
200000
180000
160000
140000
120000 267
100000
129
80000
60000
40000 185
87
20000 241
108 150
167 204222 313331 357 388 413432450
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 559 -
PVC99
Abundance

340000 57
320000
300000
280000
260000
240000
220000
200000
180000 99
160000
169
140000
120000
241
100000
80000
60000
151
40000 297
126
20000 197 315
81 261 353
223 371
279 335 401 431450
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC100
Abundance

155
500000
55
450000
400000
88
350000
300000
250000
200000 109
150000
206
100000
136
50000 188
262 318
281 346 374
237 406426 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 560 -
PVC101
Abundance

88
900000
800000
700000
600000
500000
400000
340
300000
200000 157
297
100000 61 115
213 241
135 185 269
322 360 383401
419 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC102
Abundance

2800000
258
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
215
1000000
800000 75
600000
400000
55 101
129 287
337
200000 163
187 355
239 313 385 415 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 561 -
PVC103
Abundance

273
210000
200000
190000
180000
170000
160000
150000
185
140000
293
129
130000
120000
110000
100000
90000
80000
70000
60000
50000 219
89
40000
30000
20000 147
343 374
10000 61
315
237
393411429447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC104
Abundance

160000 286
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000
20000 315
74 257
10000
40 198
94 120 146 180 237 340 363 396417 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 562 -
PVC105
Abundance

185
650000
600000
259
550000
500000
450000
400000
129
350000
300000
250000
43
200000
150000
157
100000 219
111 363
50000 91 307
63
237 277 339 394412 437
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC106
Abundance

157
100000
95000
112
90000
85000
80000
75000
70000
65000
60000
57
55000
50000
139
45000
40000 269
35000
30000
25000
20000
15000
10000
84 212
5000
313 385
190 237 294 332 368
350 418 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 563 -
PVC107
Abundance

150
1300000
1200000
1100000
1000000
57 132
900000
800000
700000
600000
500000
400000
300000
200000
105
374
100000 83 287
213 262
181 244 317338 392
410431
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC108
Abundance

1000000 185
900000
293
800000
219
700000
600000
129
500000
400000
300000
200000
157
55 111
100000
247 363
91 273 329
73 311 394 421 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 564 -
PVC109
Abundance

140000 57
130000
120000
110000
100000
90000
80000
85
70000
60000
50000
40000
309
30000
20000 113
10000 141 337

169
197 225 253 281 416
358 383 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC110
Abundance

131
1500000
1400000
1300000
1200000
1100000 408
1000000
900000
800000
219
700000
600000
500000
400000 101
57 337
300000
161
200000 189
75
245263
100000
309
281 366384 426 449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 565 -
PVC111
Abundance

185
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000 323
155
15000
55 343
10000 369
109
81
5000 223
255 295
137 205 277 416
387 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC112
Abundance

155
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
109
6000
5000 129
67
4000
3000 203
2000
315 341 369
1000 88 265 431
45 180 222242 294 403
449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 566 -
PVC113
Abundance

130
1100000
1000000
900000
800000
700000
600000
500000
400000
371
300000
101 239
200000
55 315
75
100000 190
257 343
149 172 218 287 389410429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC114
Abundance
Average of 21.737 to 21.770 min.: Average of 21.780 to 21.808 min.: RXN_LSCREEN (+)
8500000 155
8000000 55
7500000
7000000
6500000
6000000
5500000
83
5000000
4500000
4000000 109
3500000
3000000
2500000
2000000
1500000
1000000 137 201

229
500000
183 259 295
277 327 355 387 415434
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 567 -
PVC115
Abundance

185
800000
700000
315
600000
129
500000 57 203
400000
300000
157 273
200000
100000
102 241
84 347
222 297 369 399
417 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC116
Abundance

149
1600000
1500000
1400000
1300000
1200000
1100000
1000000
900000
800000
700000
600000
167
500000
400000
300000
279
70
200000
41 104
100000
122
194 221239 261 314
297 333 356 380 410429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 568 -
PVC117
Abundance

57
2600000
2400000
2200000
2000000
1800000
1600000
164
1400000 182
1200000
1000000 276
406
800000
600000 113 137
400000
294
200000 83
250
204 232 315334354 380 431450
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC118
Abundance

131
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000 101
60000
55
40000
75
203 265 412
20000
151
173 221 246 287 316 341 369387 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 569 -
PVC119
Abundance

129
340000
320000
300000
280000
260000
229
240000
220000
200000
55
180000 83
160000
140000
155
120000
100000
80000
109
60000
40000
193 337
20000 211
295
175 263 358
319 387405 429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC120
Abundance

120000 159
110000
100000
90000
80000
70000
60000
50000
239
40000
30000
98 117
20000 351
177
10000
311
40 74 269 383
135 198218 293 333 401
419 443
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 570 -
PVC121
Abundance

149
130000
120000
110000
100000
90000
80000
70000
60000
50000
167
40000 57 293
83
30000
127
20000
10000 207
104
185 248267
230 312331350 378 400419 446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC122
Abundance

180000 71
149
170000
160000
43
150000
140000
130000
120000
110000
100000
90000
80000
70000
351
60000
50000
293
127
40000
97 167
30000
20000
10000 322
207 379
225 253 275 415
189 397 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 571 -
PVC123
Abundance

149
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
293
80000
57
60000
85 127
40000
167
20000
104
207 275
185 228248 312333355 378 401 429449
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC124
Abundance

550000 149
500000
450000
400000
350000
300000
250000
200000
150000 293
100000
71
43 127
50000 167
104 275
185 207 230250 320342361 387 418436
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 572 -
PVC125
Abundance

220000
149
200000
180000
160000
140000
120000
100000
80000
60000
293
40000
249
20000 121 187
93 275
52 170 205 231 325 352 389 414 440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC126
Abundance

149
220000
200000
180000
160000
140000
120000
100000
293
80000
60000
40000 71
43 127
20000 167
104
252 275
193213234 311 333 367386 413 447
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 573 -
PVC127
Abundance

36000 83
34000
32000
30000
28000
26000
24000
271
22000 327
20000 225
18000
253
16000 55
14000
12000
110
10000
8000 148
392
6000
4000 207
181 364
2000 309
290 345 427446
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC128
Abundance

400000 149
380000
360000
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000
57
120000
100000
293
80000 85
60000
40000 127
20000
104 167 190 337 379
275 410
208229247 312 361 429448
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 574 -
PVC129
Abundance

293
10000
9500
9000
8500
207
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500 73
275
2000 127147
1500 420
179 361
1000 231
337 384
500 52 104 251 449
312
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC130
Abundance

57
280000
260000
240000
220000
200000 149
180000
160000
140000
85 379
120000
100000
80000
60000
293
40000 127
20000
169 351
197
109 219239 275
258 323 401419 445
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 575 -
PVC131
Abundance

170000 57 155
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000 113
50000 81
40000
30000
20000 194
173
137
10000 277
247 295 393 420
219 323343363 440
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC132
Abundance

110000 57
100000
90000
80000
70000
60000 83
50000
207
40000
30000
20000 281
112
159
365
10000 341 392
233 255 420
133 188 307 441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 576 -
PVC133
Abundance

57
75000
70000
65000
60000
55000
50000 83
45000
40000
35000 207
30000
25000
20000 281
112
15000 147
10000 351 434
5000 401
251 327
169
189 229 308 378
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC134
Abundance

57
100000
95000
90000
85000
80000
75000
70000
65000
60000
295
55000
207
341
50000
313
45000
40000
35000 267
149
406
30000 434
177
249
25000
20000 369
15000
123
10000 85
105
5000
225 387
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 577 -
PVC135
Abundance

57
110000
100000
90000
80000
70000 295
341
60000 207 313
50000
397
40000 267
30000 149 177 249

85 369 434
20000 126
10000 105 415

231
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC136
Abundance

120000 57
110000
100000
90000
80000
295
70000
60000
313
50000
40000 434
341
149 406
30000 267
177
83 221 249 369
20000 195
123
10000 105
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 578 -
PVC137
Abundance

20000 73 207
19000
18000
97
17000
281
16000
15000
14000
13000 147
12000
11000
10000
9000
8000
7000
6000
355
5000
243
4000
299
3000
401
2000 128 187 225 441
52
329 383
1000 420
261
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC138
Abundance

26000 57
25000
24000 97
23000
313
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000 295
12000
11000
10000
9000
434
8000
7000
369
6000
5000
249 334
4000
408
3000 277
127 149167
2000 230
79
1000 185 211
390
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 579 -
PVC139
Abundance

57
600000
550000 313
295
500000
450000
400000
434
350000 267
300000
250000
200000
149 207 249

150000 177 407
369
334
100000
123
50000
79 105
231 387
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC140
Abundance

2000000
57
313
1800000
1600000
1400000
295
1200000
1000000 434
369
800000
267 334
600000 149
177 221
408
239
400000
195
123
200000
79 105
387
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 580 -
PVC141
Abundance

850000
313
800000
750000
700000
650000 57
600000
295
550000
500000
450000
400000
350000
300000
434
250000
200000 369
267
249
150000 149
177 334
221 408
100000 195
123
50000
79 105
387
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC142
Abundance

207
100000
90000 295
80000
70000
73
60000
50000
40000
30000 41 313
267 434
147 341
20000
177 369
249
393
10000 96 415
123
230
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 581 -
PVC143
Abundance

240000 432
220000
200000
180000
160000
140000
120000
100000
80000
60000
91 342
40000 119
20000
165 370
65 145 191
40 209 241 265
283 314 388406
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC144
Abundance

57
280000
260000
240000
220000
200000
180000
160000 85
140000
120000
100000
80000
60000
40000 113
20000 141
169 197 267
239 309 351 393 421 449
221 290 330 369
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 582 -
Mass spectra of the peaks detected in the extracts of the PA + additive samples
that were not present in the PA samples
No additional peaks detected
- 583 -
APPENDIX 1
The additives used in the preparation

of the test materials
- 584 -
Synonyms, CAS numbers, molecular weights, compound classifications, structures and
any current (April 2007) European legislative restrictions for the additives used in the
manufacture of the six materials are described in this Appendix.
1. Polypropylene
The ingredients and processing aids used in the manufacture of the polypropylene test
material are:
Nucleating agent Diparamethyldibenzylidene sorbitol

Antioxidants Tris(2,4-di-tert-butylphenyl)phosphite
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-
triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-
piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-
tetramethyl-4-piperidinyl)imino]]
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine
ethanol-alt-1,4-butanedioic acid)
Slip agents Erucamide
Anti-static agents Glycerol monostearate
Filler Calcium carbonate
- 585 -
DIPARAMETHYLDIBENZYLIDENE SORBITOL
Synonyms: Bis(methylbenzylidene) sorbitol
CAS Number: 54686-97-4

81541-12-0
87826-41-3
69158-41-4
Molecular weight: 386 g/mol
Classification Sorbitol based
Structure:
O
O CH3
H3C O
OH
HO
Legislative restriction(s): Diparamethyldibenzylidene sorbitol is listed in the

Synoptic Document.
This substance is on SCF List 2.
Group TDI: 1 mg/kg b.w. (with bis(4-
ethylbenzylidene)sorbitol and dibenzylidene sorbitol).
28- and 90-day oral rat studies, one in-vitro mutagenicity
study. See references for bis(4-ethylbenzylidene)sorbitol.
- 586 -
TRIS(2,4-DI-t-BUTYLPHENYL) PHOSPHITE
Synonyms: Phosphorous acid, tris(2,4-di-tert-butylphenyl) ester
Molecular weight: 646.9 g/mol
Classification Aryl phosphite
Structure:
CH3
H3C CH3
CH3 CH3
H3C CH3
CH3
O O H3C
P
H3C
O
H3C H3C CH3

CH3
H3C CH3
CH3 H3C
Legislative restriction(s): Tris(2,4-di-t-butylphenyl) phosphite is listed in the

Synoptic Document.
The EFSA/SCF opinion states ‘TDI: 1 mg/kg b.w. 90-day
and 2-year oral rat studies, 2-generation study in rats and
mutagenicity studies. (HRC report CBG 167/76339, 18
Aug.1976, LSR 80/CIA 015/111, 21 Oct. 1980, Ciba-
Geigy 82 0873 Feb. 1985).’
- 587 -
PENTAERYTHRITYL TETRAKIS [3-(3´,5´-DI-T-BUTYL-4-HYDROXYPHENYL)
PROPIONATE]
Synonyms: Tetrakis [methylene (3,5-di-tert-butyl-4-
hydroxyhydrocinnamate)] methane
Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl)-4-
hydroxy-
2,2-Bis ((3-(3,5-bis (1,1-dimethylethyl)-4-hydroxyphenol)-
1-oxopropoxy) methyl)-1,3-propanediyl ester;
Pentaerythritol tetrakis (3,5-di-t-butyl)-4-
hydroxyhydrocinnamate;
Tetrakis [methylene-3(3´,5´-di-t-butyl-4-hydroxyphenyl)
propionate] methane;
Pentaerythrityl tetrakis [3-(3´,5´-di-t-butyl-4-
hydroxyphenyl) propionate]
Classification Sterically hindered phenol

Structure:
HO t-Bu
t-Bu
t-Bu
OH
O
O t-Bu
O O O
O
O
O
t-Bu
t-Bu
t-Bu OH
HO
t-Bu
Legislative restriction(s): Tetrakis [methylene (3,5-di-tert-butyl-4-

hydroxyhydrocinnamate)] methane is listed in the
Synoptic Document.
- 588 -
The EFSA/SCF opinion states ‘TDI: 3 mg/kg b.w. Oral
studies for 3 months and 2 years in rats, 3 and 4 months
in dogs, lifetime in mice, reproduction and teratogenicity
in mice and rats and mutagenicity studies. (RIVM report
89/678608/013, 1989-06-13).’
- 589 -
POLY [[6-[(1,1,3,3-TETRAMETHYLBUTYL) AMINO]-S-TRIAZINE-2,4-DIYL] [2,2,6,6-
TETRAMETHYL-4-PIPERIDYL) IMINO] HEXAMETHYLENE [(2,2,6,6-
TETRAMETHYL-4-PIPERIDYL) IMINO]]
Synonyms: N,N´-Bis (2,2,6,6-tetramethyl-4-piperidinyl)-1,6-
hexanediamine, polymer with 2,4,6-trichloro-1,3,5-triazine
and 2,4,4-trimethyl-1,2-pentanamine,

71878-19-8
Molecular weight: Typically 2000 g/mol
Classification Oligomeric hindered amine
Structure:
CH3 H CH3
H3C N CH3
N N
N
N N
NH
H3C N CH3 tert.Oct
CH3 H CH3
n
Legislative restriction(s): Poly [[6-[(1,1,3,3-tetramethylbutyl) amino]-s-triazine-2,4-

diyl] [2,2,6,6-tetramethyl-4-piperidyl) imino]
hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] is
listed in the Synoptic Document.
The EFSA/SCF opinion states ‘TDI: 0.05 mg/kg b.w. 3-
month oral dog and 3- and 6-month oral rat studies,
mutagenicity studies. (RIVM rep.89/678608/006 1989-
04-11).’
A specific migration limit (SML) of 3 mg/kg has been
assigned.
- 590 -
POLY(4-HYDROXY-2,2,6,6-TETRAMETHYL-1-PIPERIDINE ETHANOL-ALT-1,4-
BUTANEDIOIC ACID)
Synonyms: Dimethyl succinate polymer with 4-hydroxy-2,2,6,6-
tetramethyl-1-piperidine ethanol
1-(2-Hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl
piperidinesuccinic acid, dimethyl ester, copolymer
Poly/(2,2,6,6-tetramethylpiperidine-1,4-diyl)
ethyleneoxysuccinyloxyl
Dimethylsuccinate/tetramethyl hydroxy-1-hydroxyethyl
piperidine polymer
Molecular weight: Typically 3500 g/mol
Classification: Polymeric hindered amine
Structure:
CH3 O
H3C
O
N
O
O CH3
CH3
n
Legislative restriction(s): Dimethylsuccinate/tetramethyl hydroxy-1-hydroxyethyl

piperidine polymer is listed in the Synoptic Document.
The EFSA/SCF opinion states ‘TDI : 0.5 mg/kg b.w. 90-
Day oral rat and dog studies, 2-year oral rat study. (HRC
report CBG 237/92271, 10 May 1983).’
assigned.
- 591 -
ERUCAMIDE
Synonyms: Erucic acid amide
Erucylamide
Docosenamide
13-Docosenamide
cis 13-Docosenamide
Classification: Aliphatic amide
Structure:
NH2
H3C
Legislative restriction(s): The SCF opinion on erucamide in the Synoptic Document

lists the substance as being assigned to SCF List 3 and
that it hydrolyses to innocuous substances. (RIVM doc.
1990-09-12, CS/PM/2434).
Erucamide is listed in the Synoptic Document.
The EFSA/SCF opinion states ‘Hydrolyses to innocuous
substances. Available: Migration data, Ames test,
hydrolysis tests. (RIVM doc. 1990-09-12, CS/PM/2434).’
- 592 -
GLYCEROL MONOSTEARATE
Synonyms: GMS
2,3-Dihydroxypropyl octadecanoate
Glycerin monostearate
Glycerol stearate
Glycerol stearate
Monostearin
Octadecanoic acid monoester with 1,2,3-propanetriol
1,2,3-Propanetriol octadecanoate
Stearic acid, monoester with glycerol
Stearic monoglyceride
CAS Number: 123-94-4 (pure grade)

11099-07-3 (crude grade)
31566-31-1 (generic)
85666-92-8 (generic)
85251-77-0
Classification: Aliphatic carboxylic acid ester
Structure:
O
HO O CH3
OH
Legislative restriction(s): Glycerol monostearate is listed in the Synoptic

Document.
The EFSA/SCF opinion states ‘ADI : not specified
(JECFA 17M., 1973).’
- 593 -
CALCIUM CARBONATE
Synonyms: Allied whiting
Carbonic acid calcium salt
Monocalcium carbonate
Pigment white 18
Precipitated calcium carbonate
Precipitated chalk
Prepared chalk
Vienna white
White powder
Whiting
Classification: Inorganic salt
Structure: CaCO3
Legislative restriction(s): Calcium carbonate is not listed in the Synoptic

Document.
- 594 -
2. High density polyethylene
The ingredients and processing aids used in the manufacture of the polyethylene test
material are:
Antioxidants Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-
diylphosphonite
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate
Slip agents Oleamide
Inorganic colourants Titanium dioxide
Anti-static agents N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine
Lubricants Glycerol monooleate
Sodium (C10-C18) alkyl sulfonate
Optical brightener 2,5-Bis(5'-tert-butylbenzoxazol-2-yl)thiophene
- 595 -
TETRAKIS (2,4-DI-TERT-BUTYL-PHENYL) 4,4'-BIPHENYLENE-DIPHOSPHONITE
Synonyms: Phosphonous acid, (1,1´-biphenyl)-4,4´-diylbis-,
Tetrakis (2,4-bis (1,1-dimethylethyl) phenyl) ester;
Tetrakis (2,4-di-t-butylphenyl)-4,4´-biphenylene
diphosphite,
Phosphorus trichloride, reaction products with 1,1´-
biphenyl
2,4-bis (1,1-dimethylethyl) phenol,
Di-t-butylphenyl phosponite condensation product with
biphenyl

119345-01-6
Classification: Aryl phosphonite
Structure:
H3C CH3
H3C CH3 H3C CH3
H3C CH3 H3C CH3
O O
H3C P P CH3
O O
H3C CH3
H3C CH3 H3C CH3
CH3 H3C
H3C CH3 H3C CH3
Legislative restriction(s): Tetrakis (2,4-di-tert-butyl-phenyl) 4,4'-biphenylene-

diphosphonite is listed in the Synoptic Document.
day oral rat study and mutagenicity studies. (Sandoz
report 1979).’
assigned.
- 596 -
OCTADECYL 3,5-DI-T-BUTYL-4-HYDROXYHYDROCINNAMATE
Synonyms: Octadecyl 3,5-bis (1,1-dimethylethyl)-4-hydroxybenzene
propanoate,
Octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate
Stearyl-3-(3´,5´-di-t-butyl-4-hydroxyphenyl) propionate
Classification: Hindered phenol
Structure:
CH3 O
CH3
C18H37
H3C O
HO
H3C
H3C CH3
Legislative restriction(s): Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate is

listed in the Synoptic Document.
The EFSA/SCF opinion states ‘TDI: 0.1 mg/kg b.w.
Several oral rat studies (3-weeks to 3-months), 2-year
oral studies in mice and rats, two-generation and
teratogenicity studies, mutagenicity tests. (RIVM doc. 31-
03-92).’
assigned.
- 597 -
OLEAMIDE
Synonyms: 9-Octadecenamide
Oleic acid amide
Oleyl amide
Classification: Aliphatic amide
Structure:
H3C
NH2
Legislative restriction(s): Oleamide is listed in the Synoptic Document.

The EFSA/SCF opinion states ‘Hydrolyses to innocuous
substances. Available: Migration data, Ames test,
hydrolysis tests. (RIVM doc. 1990-09-12, CS/PM/2434).’
- 598 -
TITANIUM DIOXIDE
Synonyms: CI 7789
Pigment white 6
Titania
Titanic acid anhydride
Titanic anhydride
Titanic earth
Titanic oxide
Titanium oxide
Titanium peroxide
Titanium white

13463-67-7
Classification: Inorganic oxide
Structure: TiO2
Legislative restriction(s): Titanium dioxide is listed in the Synoptic Document.

The EFSA/SCF opinion states ‘Acceptable. (SCF, 1st
Series, 1975).’
- 599 -
N,N-BIS-(2-HYDROXYETHYL)ALKYL(C13-C15)AMINE
Synonyms: Bis (2-hydroxyethyl) cocamine
Bis (2-hydroxyethyl) cocoamine
PEG 100 coconut amine
POE (2) coconut amine
PEG-2 cocamine
Molecular weight: 287-315 g/mol
Classification: Ethoxylated amines
Structure:
OH
R N
OH
R = C13-C15
Legislative restrictions: Bis (2-hydroxyethyl) cocamine is listed in the Synoptic

Document.
This substance is on SCF List 9 and SCF List W
(different entries for the same CAS number).
- 600 -
GLYCEROL MONOOLEATE
Synonyms: Glyceryl oleate
Glycerin monoleate
Glycerol monoleate
Glycerol monooleate
Glycerol oleate
Glyceryl monooleate
Monoglyceryl oleate
Monoolein
Monooleoylglycerol
9-Octadecenoic acid, monoester with 1,2,3-propanetriol
Oleic acid glycerol monoester
Oleic acid monoglyceride
Oleoylglycerol
Oleylmonoglyceride
CAS Number: 111-03-5; 25496-72-4 (generic)

37220-82-9
68424-61-3 (generic);
Classification: Aliphatic carboxylic acid ester
Structure:
O
HO O CH3
OH
Legislative restriction(s) Glycerol monooleate is listed in the Synoptic Document.

The EFSA/SCF opinion states ‘ADI : not specified
(JECFA 17M., 1973).’
- 601 -
SODIUM (C10-C18) ALKYL SULFONATE
Synonyms: Alkylaryl sodium sulfonate
n-Alkyl (C10-18) sulfonic acids, sodium salts
C10-18-alkane sulfonate, sodium salt
(C10-C18) alkylsulfonic acid, sodium salt
Sulfonic acids, C10-18-alkane, sodium salts
Molecular weight: 260 – 372 g/mol
Classification Alkyl sulfonates
Structure: O O
-
R S
Legislative restriction(s) Sodium C10-C18 alkyl sulfonate is listed in the Synoptic

Document.
This substance is on SCF List W9 (Substances and
groups of substances which could not be evaluated due
to lack of specifications (substances) or to lack of an
adequate description (groups of substances).
- 602 -
2,5-BIS(5'-TERT-BUTYLBENZOXAZOL-2-YL)THIOPHENE
Synonyms: 2,2´-(2,5-Thiophenediyl) bis [5-t-butylbenzoxazole]
BBOT
Benzoxazole 2,2´-(2,5-thiophenyl)-bis-5-(1,1-
dimethylethyl)-
2,5-Bis (5-t-butyl-2-benzoxazol-2-yl) thiophene
Classification: Bis (benzoxazolyl) derivative
Structure:
O N
S
CH3
H3C N O
CH3 CH3
H3C
CH3
Legislative restriction(s): 2,5-Bis(5'-tert-butylbenzoxazol-2-yl)thiophene is listed in

the Synoptic Document.
day oral dog and rat studies, 1-year (+ 0.5-year recovery)
study in mice showed accumulation in tissues by
fluorescence. (RIVM, doc. tox. 300/277, June 1981).’
An SML of 0.6 mg/kg has been assigned.
- 603 -
3. Polystyrene
The ingredients and processing aids used in the manufacture of the polystyrene test
material are:
Antioxidants Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-
m-tolyl)-propionate)
Tris(nonylphenyl)phosphite
Processing aids / flow
Di-(2-ethylhexyl) phthalate
promoters
Mould release agents N,N-Bis(stearoyl)ethylenediamide
Emulsifiers Polyethylene glycol 4-tert-octyl-phenyl ether, n~5
Polyethylene glycol 4-tert-octyl-phenyl ether, n=9-10
UV absorber 2-(2’-Hydroxy-5’-methylphenyl)benzotriazole
- 604 -
ETHYLENEBIS(OXYETHYLENE)BIS-(3-(5-TERT-BUTYL-4-HYDROXY-M-TOLYL)-
PROPIONATE)
Synonyms: Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl)-4-
hydroxy-, 1,2-ethanediylbis (oxy-2,1-ethanediyl) ester
3,5-Bis (1,1-dimethylethyl)-4-hydroxy-, 1,2-ethanediylbis
(oxy-2,1-ethanediyl) ester benzenepropanoic acid
Benzenepropanoic acid, 3-(1,1-dimethyl)-4-hydroxy-5-
methyl-1,2-ethanediyl bis (oxy-2,1-ethanediyl) ester
Triethylene glycol bis (3-t-butyl-4-hydroxy-5-
methylhydrocinnamate)
Triethylene glycol bis (3-t-butyl-4-hydroxy-5-
methylphenyl) propionate
Triethylene glycol bis [3-(3-t-butyl-4-hydroxy-5-
methylphenyl) propionate
Ethylenebis (oxyethylene) bis (3-t-butyl-4-hydroxy-5-
methylhydrocinnamate)
Classification Sterically hindered phenol
Structure:
CH3
OH
CH3 O
CH3
O O CH3
H3C O O
H3C
O CH3
HO
CH3
Legislative restriction(s): Ethylenebis (oxyethylene) bis (3-t-butyl-4-hydroxy-5-

methylhydrocinnamate) is listed in the Synoptic
Document.
The EFSA/SCF opinion states ‘SCF_list: 2 TDI = 0.15
mg/kg b.w. See SCF evaluation in the website:
http://europa.eu.int/comm/food/fs/sc/scf/out140_en.pdf’
An SML of 9 mg/kg has been assigned.
- 605 -
TRIS(NONYLPHENYL)PHOSPHITE
Synonyms: TNPP
Nonylphenyl phosphite (3:1)
Phenol, nonyl-, phosphite (3:1)
Classification Phosphite triester of nonyl phenol
Structure:
C9H19
P O
H19C9 O
C9H19
Legislative restriction(s): Tris(nonylphenyl)phosphite is not listed in the Synoptic

Document.
- 606 -
DI-(2-ETHYLHEXYL) PHTHALATE
Synonyms: DEHP
1,2-Benzenedicarboxylic acid, bis (2-ethylhexyl) ester
Bis (2-ethylhexyl)-1,2-benzenedicarboxylate
Bis (2-ethylhexyl) phthalate
Di (2-ethylhexyl) orthophthalate
Dioctyl phthalate
Di-s-octyl phthalate
Ethylhexyl phthalate
2-Ethylhexyl phthalate
Phthalic acid, bis (2-ethylhexyl) ester
Phthalic acid dioctyl ester
s-Dioctyl phthalate
Classification Diester of 2-ethylhexyl alcohol and phthalic acid
Structure: O
C2H5
O
C 4H9
C2H5
O O
C4H9
Legislative restriction(s): Di-(2-ethylhexyl) phthalate is listed in the Synoptic

Document.
The EFSA/SCF opinion states ‘Under re-evaluation. TDI:
0.05 mg/kg b.w. (see the individual report, CS/PM/2161
FINAL).’
Commission Directive 2007/19/EC, amending Directive
2002/72/EC states that DEHP is:
- 607 -
To be used only as:
(a) plasticizer in repeated use materials and articles
contacting non-fatty foods;
(b) technical support agent in concentrations up to 0,1 %
in the final product.
SML = 1.5 mg/kg food simulant.
- 608 -
N,N-BIS(STEAROYL)ETHYLENEDIAMIDE
Synonyms: Ethylene distearamide
1,2-Bis (octadecanamido) ethane
1,2-Bis (stearoylamino) ethane
N,N´-Distearoylethylenediamine
N,N´-1,2-Ethanediylbisoctadecanamide
Ethylene bis (stearamide)
N,N´-Ethylene bisstearamide
Ethylenebisstearoamide
Ethylenebis (stearylamide)
Ethylenediamine bisstearamide
Ethylenediamine steardiamide
N,N´-Ethylenedistearamide
N,N´-Ethylene distearylamide
Octadecanamide, N,N´-1,2-ethanediylbis-
Octadecanamide, N,N´-ethylenebis-
Stearic acid, ethylenediamine diamide

68955-45-3
Classification Diamide
Structure:
O
NH C17H35
H35C17 NH
Legislative restriction(s): N,N-Bis(stearoyl)ethylenediamide is listed in the Synoptic

Document.
The EFSA/SCF opinion states ‘Two inadequate 2-year
oral rat studies and low migration (Hoechst report 13/05,
1963).’
- 609 -
POLYETHYLENE GLYCOL 4-TERT-OCTYL-PHENYL ETHER, n~5
AND
POLYETHYLENE GLYCOL 4-TERT-OCTYL-PHENYL ETHER, n=9-10
Synonyms: Octoxynol
Glycols, polyethylene, mono (p-(1,1,3,3-tetramethylbutyl)
phenyl) ether
Octyl phenol EO condensate
Octyl phenol ethoxylates
p-t-Octylphenoxypolyethoxyethanol
PEG octyl phenyl ether
Polyethylene glycol monoether with p-t-octylphenyl
Polyethylene glycol mono (4-octylphenyl) ether
Polyethylene glycol mono (p-t-octylphenyl) ether
Polyethylene glycol mono (4-t-octylphenyl) ether
Polyethylene glycol mono (p-(1,1,3,3-tetramethylbutyl)
phenyl) ether
Polyethylene glycol octylphenol ether
Polyethylene glycol p-octylphenyl ether
Polyethylene glycol p-t-octylphenyl ether
Polyethylene glycol p-1,1,3,3-tetramethylbutylphenyl
ether
Polyoxyethylene mono (octylphenyl) ether
CAS Number: 9002-93-1 (generic)

9010-43-9
Molecular weight: 426 - 646 g/mol (n = 5 – 10)
Classification Ethoxylated alkyl phenol
Structure:
H17C8 O
OH
n n = 5 - 10
Legislative restriction(s): Polyethyleneglycol octylphenyl ether is listed in the

Synoptic Document.
- 610 -
- 611 -
2-(2’-HYDROXY-5’-METHYLPHENYL)BENZOTRIAZOLE
Synonyms: 2-(2H-Benzotriazole-2-yl)-4-methylphenol
2-(2H-Benzotriazol-2-yl)-p-cresol
2-(2H-Benzotriazol-2-yl)-4-methylphenol
2-(2´-Hydroxy-5´-methylphenyl) benzotriazole
Drometrizole
Classification Benzotriazole derivative

Structure:
HO
CH3
Legislative restriction(s): 2-(2’-Hydroxy-5’-methylphenyl) benzotriazole is listed in

the Synoptic Document.
The EFSA/SCF opinion states ‘Group TDI: 0.5 mg/kg
b.w. for 2-(2'-hydroxy-3'-tert.butyl-5'-methylphenyl)-5-
chlorobenzotriazole, 2-(2'-hydroxy-3,5'-ditert.butylphenyl)-
5-chloro-benzotriazole and 2-(2'-hydroxy-5'-
methylphenyl)benzotriazole. Several 90-day oral rat and
dog studies and a 2-year oral rat study and 3-4 month
oral dosing of man. (HRC report CBG 161/78164).’
An SML(T) of 30 mg/kg (with 2-(2'-hydroxy-3,5'-
ditert.butylphenyl)-5-chloro-benzotriazole) has been
assigned.
- 612 -
4. Polyethylene terephthalate
The ingredients and processing aids used in the manufacture of the polyethylene
terephthalate test material are:
Stabiliser 2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1-
phenylethyl)phenol
Acetaldehyde scavanger Hexanedioic acid polymer with 1,3-
Colourant Copper phthalocyanine blue
- 613 -
2-(2H-BENZOTRIAZOL-2-YL)-4,6-BIS (1-METHYL-1-PHENYLETHYL) PHENOL
Synonyms: 2-[2-Hydroxy-3,5-di-(1,1-dimethylbenzyl) phenyl]-2H-
benzotriazole
2-(Benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl)
phenol
2-[2´-Hydroxy-3´,5´-bis (1-methyl-1-phenylethyl)]
benzotriazole
Classification Benzotriazole derivative

Structure:
H3C
HO
N CH3
H3C
H3C
Legislative restriction(s): 2-[2-Hydroxy-3,5-di-(1,1-dimethylbenzyl) phenyl]-2H-

benzotriazole is listed in the Synoptic Document.
day oral rat study, 3 mutagenicity studies. (RIVM doc. 27
October 1987).’
An SML of 1.5 mg/kg has been assigned.
- 614 -
HEXANEDIOIC ACID POLYMER WITH 1,3-BENZENEDIMETHANAMINE
Synonyms: Nylon MXD6
Molecular weight: Not defined
Classification Amide polymer
Structure:
H OH
NH NH
Legislative restriction(s): Nylon MXD6 is listed in the Synoptic Document.

The EFSA/SCF opinion states ‘Available: Range of
numerical molecular mass (Mn): 14.000 - 21300 D.
Needed: Mw distribution curve. (CS/PM/2632).’
- 615 -
COPPER PHTHALOCYANINE BLUE
Synonyms: CI 74160
Copper phthalocyanine
Phthalocyanine blue
Pigment blue 15
Chromophtal Blue BCN
Classification Phthalocycanine complex
Structure:
NH N
N Cu N
N NH
Legislative restriction(s): Copper phthalocyanine blue is listed in the Synoptic

Document.
- 616 -
5. Polyvinylchloride
The ingredients and processing aids used in the manufacture of the polyvinyl chloride
test material are:
Stabilisers Dioctyltin bis(ethylmaleate)

Dioctyltin bis(2-ethylhexyl thioglycolate)
Epoxidised soya bean oil
Emulsifier Stearic acid
Plasticiser Acetyl tributyl citrate
Lubricant Paraffin wax
- 617 -
DIOCTYLTIN BIS(ETHYL MALEATE)
Synonyms: 3,8,10-Trioxa-9-stannatetradeca-5,12-dien-14-oic acid,
9,9-dioctyl-4,7,11-trioxo-, ethyl ester
Dioctylbis(3-carboxyacryloyloxy)stannane, diethyl ester
Stannane, dioctylbis[(3-carboxyacryloyl)oxy]-, diethyl
ester
Classification Organotin compound
Structure:
O O CH3
H3C
O O O
O Sn C8H19
O C8H19
O
Legislative restriction(s): Dioctyltin bis(erthylmaleate) is listed in the Synoptic

Document.
The EFSA/SCF opinion states ‘Group-TDI: 0.0006 mg/kg
bw (as Sn) for all di-n-octyltin derivatives. See references
for 50480.
An SML(T) of 0.04 mg/kg (expressed as tin) has been
assigned. SML(T) in this specific case means that the
restriction shall not be exceeded by the sum of the
migration levels of the following substances mentioned as
reference Nos: 50160, 50240, 50320, 50360, 50400,
50480, 50560, 50640, 50720, 50800, 50880, 50960,
51040 and 51120 (reference Nos as in Synoptic
Document).
- 618 -
DIOCTYLTIN BIS(ETHYLHEXYL MERCAPTOACETATE)
Synonyms: 2-Ethylhexyl 10-ethyl-4,4-dioctyl-7-oxo-8-oxa-3,5-dithia-4-
stannatetradecanoate
8-Oxa-3,5-dithia-4-stannatetradecanoic acid, 10-ethyl-
4,4-dioctyl-7-oxo-, 2-ethylhexyl ester
Classification Organotin compound
Structure:
CH3
C 4H 9
O O
O S Sn C 8H 19
C 8H 19
O
H3C C 4H 9
Legislative restriction(s): Dioctyltin bis(ethylhexyl mercaptoacetate) is listed in the

Synoptic Document.
The EFSA/SCF opinion states ‘Group-TDI: 0.0006 mg/kg
bw (as Sn) for all di-n-octyltin derivatives. See references
for 50480.
An SML(T) of 0.04 mg/kg (expressed as tin) has been
assigned. SML(T) in this specific case means that the
restriction shall not be exceeded by the sum of the
migration levels of the following substances mentioned as
reference Nos: 50160, 50240, 50320, 50360, 50400,
50480, 50560, 50640, 50720, 50800, 50880, 50960,
51040 and 51120. (reference Nos as in Synoptic
Document).
- 619 -
EPOXIDISED SOYA BEAN OIL
Synonyms: ESBO
Soybean oil, epoxidized
Molecular weight: Not defined
Classification Epoxy compound

Structure:
O
H3C
O
O
O O
O
O O
O
H3C O
O
O
H3C
Legislative restriction(s): ESBO is listed in the Synoptic Document.

The EFSA/SCF opinion states ‘Restriction for baby food:
http://www.efsa.eu.int/science/afc/afc_opinions/467/opini
on_afc10_ej64_epox_soyoil_en1.pdf. TDI: 1 mg/kg b.w.
Available: 15-week and 2-year oral rat studies and 1-year
oral dog study, reproduction and teratogenicity studies.
ADI's and TDI's are allocated in the light of life long
average exposure and allowing for sporadic intakes
above the set limits. For the infants, however, the actual
consumption pattern surveys have revealed intakes for
prolonged periods of time which may exceed the TDI.
(Bibra report n. 515/86; summary report prepared by UK
January 1988).’
Commission Directive 2007/19/EC, amending Directive 2002/72/EC states:
‘SML = 60 mg/kg. However in the case of PVC gaskets used to seal glass jars
containing infant formulae and follow-on formulae
as defined by Directive 91/321/EEC or containing
processed cereal-based foods and baby foods
for infants and young children as defined by
Directive 96/5/EC, the SML is lowered to 30
- 620 -
mg/kg. In compliance with the specifications laid
down in Annex V.’
Annex V specifies the ESBO should be oxirane < 8%, iodine number < 6.
ESBO is also included in Transitional Regulation 372/2007 which states:
For materials and articles intended for or brought into
contact with foods for which simulant D testing is required
by Directive 85/572/EEC SML(T) (1) (2) = 300 mg/kg of
food or food simulants or 50 mg/dm2 of the total food
contact surface of lid and sealed container.
contact with infant formulae and follow-on formulae as
defined by Commission Directive 91/321/EEC on infant
formulae and follow-on formulae and products according
to Directive 96/5/EC on processed cereal-based foods
and baby foods for infants and young children SML = 30
mg/kg of food or food simulant.
contact with all other types of foods SML(T) (2) = 60
mg/kg of food or food simulants or 10 mg/dm2 of the total
food contact surface of lid and sealed container.
- 621 -
STEARIC ACID
Synonyms: Carboxylic acid C18
1-Heptadecanecarboxylic acid
Octadecanoic acid
n-Octadecanoic acid
Pearl stearic
Stearophanic acid
CAS Number: 57-11-4

67701-03-5
Classification Fatty acid

Structure:
O
OH
H3C
Legislative restriction(s): Stearic acid is listed in the Synoptic Document.

The EFSA/SCF opinion states ‘ADI: not specified. (SCF,
25th Series, 1990).’
- 622 -
ACETYL TRIBUTYL CITRATE
Synonyms: ATBC
Acetyl butyl citrate
Acetylcitric acid, tributyl ester
2-(Acetyloxy)-1,2,3-propanetricarboxylic acid, tributyl
ester
Acetyl tri-n-butyl citrate
Citric acid, tributyl ester, acetate
1,2,3-Propanetricarboxylic acid, 2-(acetyloxy)-, tributyl
ester
Tributyl acetyl citrate
Tributyl O-acetylcitrate
Tri-n-butyl O-acetylcitrate
Tributyl 2-(acetyloxy)-1,2,3-propanetricarboxylate
Tributyl citrate acetate
Tri-n-butyl citrate acetate
CAS Number: 77-90-7
Classification Aliphatic ester

Structure:
O
O O CH3
O CH3
H3C O
O CH3
Legislative restriction(s): Acetyl tributyl citrate is listed in the Synoptic Document.

The EFSA/SCF opinion states ‘New studies on-going. R
= 5 mg/kg of food. Available: specific migration values in
3% acetic acid and olive oil ranging from 9.0-28.2 mg/6
dm2; 14-day range-finding rat study; 90-day rat study; 2-
generation reproduction study using rats; gene mutation
assay in bacteria (negative); two chromosomal aberration
- 623 -
assays in cultured mammalian cells (both negative); two
gene mutation assays in cultured mammalian cells (one
negative and one positive); in vivo UDS assay (negative);
metabolism study (rat); skin and eye irritation studies
(only summaries available); sensitisation study.
RIVM/ISS/TNO SDS, January 2000 = CS/PM/2966
REV.II/93760. Remark for Commission: since high
migration into fat has been demonstrated with the
exception of PET, it was recommended that the
Commission take the necessary measures so that the
restriction proposed is not exceeded.
- 624 -
PARAFFIN WAX
Synonyms: Hard paraffin
Paraffin waxes
Paraffin wax fume
Petroleum wax, crystalline
Poly (methylene) wax
Molecular weight Not defined
Classification Hydrocarbon
Structure: NA
Legislative restriction(s): Paraffin is listed in the Synoptic Document.

This substance is on SCF List 9 and D (two separate
entries).
The use of waxes in plastic packaging materials is
subject to Commission Directive 2002/72/EC relating to
plastic materials and articles intended to come into
contact with foodstuffs. The specification given in Annex
V of this Directive states:
“Waxes, refined, derived from petroleum based or
synthetic hydrocarbon feedstocks. The product should
have the following specifications:
- Content of mineral hydrocarbons with Carbon number
less than 25, not more than 5 % (w/w)
- Viscosity not less than 11 × 10–6 m2/s (=
11 centistokes) at 100 °C
- Average molecular weight not less than 500.”
- 625 -
6. Polyamide
The ingredients and processing aids used in the manufacture of the polyamide test
material are:
Mineral fillers Talc

Mould release agents Zinc stearate
- 626 -
TALC
Synonyms : CI 77019
CI 77718
Cosmetic talc
French chalk
Hydrous magnesium calcium silicate
Hydrous magnesium silicate
Industrial talc
Magnesium hydrogen metasilicate
Pigment white 26
Platy talc
Talcum,
Classification: Inorganic salt
Structure: 3MgO.4SiO2.H2O
Legislative restriction(s): Talc is listed in the Synoptic Document

The EFSA/SCF opinion states ‘Acceptable Daily Intake
(ADI) not specified (SCF, 25th Series, 1991).’
- 627 -
ZINC STEARATE
Synonyms: Dibasic zinc stearate
Octadecanoic acid zinc salt
Stearic acid zinc salt
Zinc distearate
Zinc octadecanoate
Zinc soap
Classification Zinc salt of stearic acid

Structure:
Zn
-
H35C17 O
2
Legislative restriction(s): Zinc stearate is not listed in the Synoptic Document.
- 628 -

Bradley and Coulier 2007

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Report FD 07/01

An investigation into the reaction and

Report Number: FD07/01

Authors - CSL: E Bradley

Date: August 2007

Project title: An investigation into the reaction and breakdown

Sponsor: Food Standards Agency

Sponsor’s Project Number: A03054

CSL Project Number: N6JF

CSL File Reference: FLN 8491

Principal Workers - CSL: E Bradley, M Driffield, S Jones, M Scotter and

Team Leader: L Castle

Distribution: 1. Dr Barnes (FSA) (x3 + .pdf version)

Six polymers were prepared containing additives chosen to be representative of those

A suite of analytical methods focussing on the analysis of substances with molecular

It is now clarified in recital 13 of Directive 2007/19/EC that there is a general

This analytical approach would provide a useful demonstration of due diligence.

ATBC Acetyl tributyl citrate

2. MANUFACTURE OF THE TEST POLYMERS

2.2 Selection of the test additives

2.2.4 Polyethylene terephthalate

2.2.5 Polyvinyl chloride

2.3 Manufacturing conditions of the test polymers

Press conditions used for PVC

Pre-heating time 4 minutes

3. IMPURITIES, REACTION PRODUCTS AND BREAKDOWN PRODUCTS OF

Photooxidation of commercial PP is probably promoted by minute traces of catalyst

3.1.2 Diparamethylenedibenzylidene sorbitol

For aromatic phosphites, like tris(2,4-di-tert-butylphenyl)phosphite, the reaction with

Another very common degradation product of tris(2,4-di-tert-butylphenyl)phosphite is

3.1.4 Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)

A variety of antioxidants have been used to inhibit degradation of thermally sensitive

In several studies degradation products of hindered phenol-type antioxidants have

Using pyrolysis GC-MS [20] on pentaerythritol tetrakis(3,5-di-tert-butyl-4-

Due to the relative high molecular weight of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-

Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) is a

The structure of poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-

No specific literature was found on possible degradation products of poly(4-hydroxy-

3.1.8 Glycerol monostearate

No literature was found on the degradation of glycerol monostearate during processing

3.1.9 Calcium carbonate

3.2 High density polyethylene

Microwave-assisted extraction was used in a comparison of virgin and recycled films

No details of any impurities, reaction products and degradation products of tetrakis(2,4-

3.2.3 Octadecyl 3,3-di-t-butyl-4-hydroxyhydrocinnamate

PP and PE plastics can be exposed to ionising radiation during sterilisation processes

3.2.5 Titanium dioxide

3.2.7 Glycerol monooleate

3.2.8 Sodium (C10-C18) alkyl sulfonate

Reprocessing of polystyrene, i.e. repeated extrusion at 190°C, induces changes in the

Thermal degradation of polystyrene has been simulated by pyrolysis GC-MS [54,55].

The light-induced degradation of commercial polystyrene is attributed to the scission of

Radiolysis products of gamma-irradiated PS were studied by GC and HPLC [57]. The

3.3.4 Di-(2-ethylhexyl) phthalate

PET is part of an important class of polyesters with a wide variety of applications.

Hydrolysis of PET is considered to be a random chain-scission reaction. The result of

During the degradation process of PET there is a change in functional group

3.4.3 Hexanedioic acid polymer with 1,3-benzenedimethanamine

Reaction and degradation products from hexanedioic acid polymer with

3.4.4 Copper phthalocyanine blue

3.5 Polyvinyl chloride

3.5.2 Dioctyltin bis(ethylmaleate) and dioctyltin bis(2-ethylhexyl thioglycolate)

Tin in the +4 oxidation state forms a large number of inorganic as well as