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.
2.
3.
4.
Dr Barnes (FSA) (x3 + .pdf version)
CSL Library
Dr Dennis (CSL)
Prof. Gilbert (CSL)
CSL
Sand Hutton
York
YO41 1LZ
-1-
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
-2-
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 wellequipped 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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Table of contents
Page No.
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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Table of contents
Page No.
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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Table of contents
Page No.
6.4.1
Additives
76
6.4.2
Samples
76
6.5
NMR analysis
77
6.5.1
Polypropylene
78
6.5.2
High density polyethylene
78
6.5.3
Polystyrene
79
6.5.4
Polyethylene terephthalate
79
6.5.5
Polyvinyl chloride
80
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
8.1.1
Polypropylene
85
8.1.2
High density polyethylene
86
8.1.3
Polystyrene
86
8.1.4
Polyethylene terephthalate
87
8.1.5
Polyvinyl chloride
87
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
-8-
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
Table 11. Proposed impurities/reaction products/breakdown products for
107
the additives used in the manufacture of the HDPE test material
Table 12. Proposed impurities/reaction products/breakdown products for
113
the additives used in the manufacture of the PS test material
Table 13. Proposed impurities/reaction products/breakdown products for
116
the additives used in the manufacture of the PET test material
Table 14. Proposed impurities/reaction products/breakdown products for
118
the additives used in the manufacture of the PVC test material
Table 15. Proposed impurities/reaction products/breakdown products for
120
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
Table 19. Substances detected in the GC-MS TIC chromatograms of the
131
ethanol extracts of the HDPE + additives samples that were not
present in the ethanol extracts of the HDPE samples
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
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140
List of Tables
Page No.
Table 21. Substances detected in the GC-MS TIC chromatograms of the
142
solvent extracts of the PET + additives samples that were not
present in the extracts of the PET samples
Table 22. Substances detected in the GC-MS TIC chromatograms of the
143
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
(final solvent acetonitrile) – substances that were only detected
in the HDPE + additives extracts
Table 35. Negative ESI analysis of the ethanol extracts of the HDPE
175
(final solvent acetonitrile) – substances that were only detected
in the HDPE + additives extracts
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
- 10 -
176
List of Tables
Page No.
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
(final solvent acetonitrile) – substances that were only
detected in the PVC + additives extracts
Table 39. Negative ESI analysis of the isooctane extracts of the PVC
183
(final solvent acetonitrile) – substances that were only
detected in the PVC + additives extracts
Table 40. Migration modelling data
184
- 11 -
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
Figure 8. Best library match of the peak eluting at retention time
192
12.9 minutes in the thermodesorption GC-MS chromatogram
of the HDPE + additives sample
Figure 9. Best library match of the peak eluting at retention time
193
7.0 minutes in the thermodesorption GC-MS chromatogram
of the PVC + additives sample
Figure 10. Best library match of the peak eluting at retention time
194
11.2 minutes in the thermodesorption GC-MS chromatogram
of the PVC + additives sample
Figure 11. Best library match of the peak eluting at retention time
195
19.1 minutes in the thermodesorption GC-MS chromatogram
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
of PP and PP + additives full scale and zoomed in to show
low intensity peaks
- 12 -
198
List of Figures
Page No.
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
Figure 21. GC-MS chromatograms of the concentrated ethanol extracts
205
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
Figure 25. GC-MS chromatograms of the concentrated ethanol extracts
209
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
of PET and PET + additives. full scale and zoomed in to show
low intensity peaks
- 13 -
210
List of Figures
Page No.
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
Figure 37. GCxGC-TOF-MS chromatograms of isooctane extracts of
221
(A) HDPE and (B) HDPE + additives
Figure 38. GCxGC-TOF-MS chromatograms of concentrated ethanol
222
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
Figure 41. GCxGC-TOF-MS chromatograms of isooctane extracts of
(A) PS and (B) PS + additives
- 14 -
225
List of Figures
Page No.
Figure 42. GCxGC-TOF-MS chromatograms of concentrated ethanol
226
extracts of (A) PS and (B) PS + additives
Figure 43. GCxGC-TOF-MS chromatograms of concentrated isooctane
227
extracts of (A) PS and (B) PS + additives
Figure 44. GCxGC-TOF-MS chromatograms of concentrated ethanol
228
extracts of (A) PET and (B) PET + additives
Figure 45. GCxGC-TOF-MS chromatograms of concentrated isooctane
229
extracts of (A) PET and (B) PET + additives
Figure 46. GCxGC-TOF-MS chromatograms of concentrated ethanol
230
extracts of (A) PA and (B) PA + additives
Figure 47. GCxGC-TOF-MS chromatograms of concentrated isooctane
231
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
Figure 56. Total ion chromatogram for HDPE and HDPE + additives
240
(ethanol extraction, final solvent acetonitrile) in positive mode
electrospray TOF-MS
Figure 57. Total ion chromatogram for HDPE and HDPE + additives
241
(isooctane extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
Figure 58. Total ion chromatogram for HDPE and HDPE + additives
(ethanol extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
- 15 -
242
List of Figures
Page No.
Figure 59. Total ion chromatogram for PVC and PVC + additives
243
(isooctane extraction, final solvent acetonitrile) in positive
mode electrospray TOF-MS
Figure 60. Total ion chromatogram for PVC and PVC + additives
244
(ethanol extraction, final solvent acetonitrile) in positive mode
electrospray TOF-MS
Figure 61. Total ion chromatogram for PVC and PVC + additives
245
(isooctane extraction, final solvent acetonitrile) in negative mode
electrospray TOF-MS
Figure 62. Total ion chromatogram for PVC and PVC + additives
246
(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
Figure 70. Stacked 1H 1D NMR spectroscopy plot of a solvent blank,
HDPE extract and HDPE + additives extract
- 16 -
254
List of Figures
Page No.
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
Figure 73. Stacked 1H 1D NMR spectroscopy plot of a solvent blank,
257
PS extract and PS + additives extract
Figure 74. Stacked 1H 1D NMR spectroscopy plot of the additives used
258
in the preparation of the PS test materials compared to the
PS extracts and PS + additives extracts
Figure 75. Stacked 1H 1D NMR spectroscopy plot of a solvent blank,
259
PET extract and PET + additives extract
Figure 76. Stacked 1H 1D NMR spectroscopy plot of the additives used
260
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
Figure 78. Stacked 1H 1D NMR spectroscopy plot of a solvent blank,
262
PVC extract and PVC + additives extract
Figure 79. Stacked 1H 1D NMR spectroscopy plot of the additives used
263
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
Figure 81. Stacked 1H 1D NMR spectroscopy plot of a solvent blank,
PA extract and PA + additives extract
- 17 -
265
List of Figures
1
Page No.
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 ethanolalt-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
Figure 85.
13
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
Figure 86.
13
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-4hydroxyhydrocinnamate), glycerol monostearate,
diparamethyldibenzylidene sorbitol and poly(4-hydroxy2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic
acid)
Figure 87.
13
C–1H HSQC NMR spectrum of the region 1H = 5.4 – 3.0
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
- 18 -
271
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
- 19 -
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.
categories of NIAS.
There are two
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
- 21 -
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 impactresistant 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 oillike 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-ditert-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
during melt processing.
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)
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]deca6,9-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].
showed
the
presence
of
pentaerythritol
PP extracts
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-tertbutyl-benzyl-methyl-propanoate
and
di-tert-butyl-quinonemethidepropionic
- 32 -
acid.
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-4hydroxyhydrocinnamate) 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-4piperidinyl)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-4piperidine.
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 GCMS 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-3,5pentadiene, 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-[(1,1,3,3tetramethylbutyl)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 2,2,6,6tetramethylpiperidine 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-hydroxy2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) in polymers during
processing or use. Some clues on possible degradation products of poly(4-hydroxy2,2,6,6-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-hydroxy2,2,6,6-tetramethyl-1-piperidene ethanol-alt-1,4-butanedioic acid) [28,29].
pyrolysis products were aza-2,2,6,6-tetramethyl-3-cyclohexene,
- 34 -
Typical
2,6-dimethyl-2,4,6-
heptatriene,
2-methyl-3,5-pentadiene,
tetramethyl-3-cyclohexeneethanol
butanedioic
and
anhydride,
1-aza-2,2,6,6-
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 byproducts 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 antistatic 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(2,4di-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.
HPLC-UV, HPLC-NMR, supercritical fluid chromatography, fluorimetry, GC-MS and
31
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-4hydroxyhydrocinnamate. 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(2,4di-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-(2hydroxyethyl)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’-tertbutylbenzoxazol-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.
impurities in styrene feedstock include toluene and xylenes.
The
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
No
Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate)
specific
information
could
be
found
on
the
degradation
ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate).
of
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-tertbutylphenol.
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 GCMS 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-(2,2,3,3tetramethyl
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 benzotriazoletype 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)
Organo-tin stabilisers are commonly added to PVC and
119
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),
ethylhexyloxycarbonyl)methanethiolate]
ethylhexyloxycarbonyl)methanethiolate].
dioctyltin
and
octyltin
bis[(2tris[(2-
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).
- 49 -
OTC have one or more
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
O
Sn 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
O
COOnBu
COOH
H2 O / H+
HO
COOnBu
3.5.6
COOH
COOH
O
+
H3C
+
3 nBuOH
OH
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 (1315%) 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:
[R´COO]2Zn + 2X´´OH 2 R´COOX´´ + 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 GCxGCTOF-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
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 15 - 800 amu.
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
10°C/minute to 320°C. The injector was held at 250 °C. Helium (1 ml/min constant
- 60 -
flow) was employed as the carrier gas. The MS was operated in electron impact mode
with scanned monitoring between 40 - 450 amu.
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. d6Benzene 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
Deerfield, IL, USA) was used.
film
thickness;
Alltech,
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.
modulation time was 4 seconds.
- 61 -
The
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 FourierTransform 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-TOFMS 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
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
C sweepwidth:
1
H – 1H Total Correlation Spectroscopy (TOCSY) spectra:
F2 1H dimension:
1
6.
15.0110 ppm
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
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-hydroxy2-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-ethyl1-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-1,4butanedioic 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-4piperidinyl)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-methyl1-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.
separated on volatility but also on polarity.
As a result compounds are not only
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 GCxGCTOF-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 GCxGCTOF-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(4hydroxy-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-(2Hbenzotriazole-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 GCMS 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-4hydroxyhydrocinnamate) and poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanolalt-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]-
[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4piperidinyl)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.
6.5.2
High density polyethylene
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-tertbutyl-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-octylphenyl
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.
6.5.4
Polyethylene terephthalate
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 -
6.5.5
Polyvinyl chloride
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.
techniques utilised were
13
The 2D NMR
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
13
C – 1H
C atom.
HSQC spectra were used to resolve peaks that overlap in the 1H 1D NMR spectrum
and to determine information about the chemical environment of the
13
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-2,2,6,6tetramethyl-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
diparamethyldibenzylidene
sorbitol,
ethanol-alt-1,4-butanedioic
pentaerythritol
acid),
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 offdiagonal 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
the non-assigned impurities were observed. The
13
C – 1H HSQC spectrum of PP
containing additives is shown in Figure 85. To determine which resonances observed
in the
13
without
C – 1H HSQC spectrum were from unidentified peaks an overlay plot of the PP
additives,
poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine
ethanol-alt-1,4-
butanedioic acid), diparamethyldibenzylidene sorbitol, pentaerythritol tetrakis(3,5-ditert-butyl-4-hydroxyhydrocinnamate)and glycerol monostearate was generated (Figure
86) and compared to Figure 85. Again these standards were chosen as they had
shown resonances in the region 2.5 – 5 ppm. Examination of the
13
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
and the
13
C information observed in the
elucidation of these compounds.
13
C – 1H HSQC spectrum would aid structural
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.
plastic/substance combinations.
This will be a large overestimation for some
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).
- 83 -
This
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
GC-MS
0 substances detected
Solvent extraction
GC-MS
55 substances detected
3 additives
17 impurities
- identities proposed for 12
- 5 predicted
35 reaction/breakdown products
- identities proposed for 15
- 5 predicted
Solvent extraction
GCxGC-MS
23 additional substances
detected (i.e. not seen by
GC-MS)
0 additives
12 derived from standards
- identities proposed for 9
- 4 predicted
11 reaction/breakdown products
- identities proposed for 4
- 0 predicted
Solvent extraction
29 substances detected
LC-MS and LC-FT-MS
3 additives
1 impurity
- identities proposed for 1
- 1 predicted
25 reaction/breakdown products
- identities proposed for 8
- 85 -
- 6 predicted
8.1.2
High density polyethylene
69 substances/classes of substances predicted from the main theoretical chemical
reaction pathways and literature searches.
The table below summarises the
substances detected in the HDPE + additive samples that were not present in the
HDPE only control samples:
Thermodesorption
GC-MS
2 substances detected
2 reaction/breakdown products
- identities proposed for 2
- 0 predicted
Solvent extraction
GC-MS
87 substances detected
4 additives
29 impurities
- identities proposed for 10
- 3 predicted
54 reaction/breakdown products
- identities proposed for 21
- 12 predicted
Solvent extraction
GCxGC-MS
0 additional substances
detected (i.e. not seen by
GC-MS)
Solvent extraction
LC-TOF-MS
26 substances detected
4 additives
6 impurities
- identities proposed for 4
- 0 predicted
16 reaction/breakdown products
- identities proposed for 14
- 2 predicted
8.1.3
Polystyrene
46 substances/classes of substances predicted from the main theoretical chemical
reaction pathways and literature searches.
The table below summarises the
substances detected in the PS + additive samples that were not present in the PS only
control samples:
Thermodesorption
GC-MS
0 substances detected
Solvent extraction
GC-MS
20 substances detected
3 additives
14 impurities
- 86 -
- identities proposed for 5
- 3 predicted
3 reaction/breakdown products
- identities proposed for 3
- 0 predicted
Solvent extraction
GCxGC-MS
0 additional substances
detected (i.e. not seen by
GC-MS)
Solvent extraction
6 substances detected
LC-MS and LC-FT-MS
8.1.4
4 additives
2 reaction/breakdown products
- identities proposed for 2
- 1 predicted
Polyethylene terephthalate
32 substances/classes of substances predicted from the main theoretical chemical
reaction pathways and literature searches.
The table below summarises the
substances detected in the PET + additive samples that were not present in the PET
only control samples:
Thermodesorption
GC-MS
0 substances detected
Solvent extraction
GC-MS
2 substances detected
Solvent extraction
GCxGC-MS
0 additional substances
detected (i.e. not seen by
GC-MS)
1 reaction/breakdown product
- identities proposed for 0
- 0 predicted
Solvent extraction
3 substances detected
LC-MS and LC-FT-MS
8.1.5
1 additive
1 additive
2 reaction/breakdown products
- identities proposed for 0
- 0 predicted
Polyvinyl chloride
30 substances/classes of substances predicted from the main theoretical chemical
reaction pathways and literature searches.
The table below summarises the
substances detected in the PVC + additive samples that were not present in the PVC
only control samples:
- 87 -
Thermodesorption
GC-MS
3 substances detected
3 reaction/breakdown products
- identities proposed for 3
- 3 predicted
Solvent extraction
GC-MS
145 substances detected* 1 additive
25 impurities
- identities proposed for 16
- 2 predicted
119 reaction/breakdown products
- identities proposed for 46
- 2 predicted
Solvent extraction
GCxGC-MS
Not analysed
Solvent extraction
LC-TOF-MS
44 substances detected
0 additives
5 impurities
- identities proposed for 0
- 0 predicted
39 reaction/breakdown products
- identities proposed for 0
- 0 predicted
* Does not include alkanes derived from the paraffin wax,
8.1.6
Polyamide
23 substances/classes of substances predicted from the main theoretical chemical
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-perbillion (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 wellequipped 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.
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- 96 -
Table 1. Formulation details of the PP test material
CAS number
PP
Use
Level (wt %)
Base polymer
65.4
Purity
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-4hydroxyhydrocinnamate)
6683-19-8
Antioxidant
0.5
98%
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]],
Mn ca. 2000
71878-19-8
Light stabiliser
1.0
Not given
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4butanedioic acid), Mn ca. 3500
65447-77-0
Light stabiliser
1.0
Not given
112-84-5
Slip agent
0.1
> 97%
31566-31-1
Anti-static agent
1.0
90+%
471-34-1
Filler
30
99+%
Erucamide
Glycerol monostearate
Calcium carbonate
- 97 -
Table 2. Formulation details of the HDPE test material
CAS number
HDPE
Use
Level (wt %)
Base polymer
92.35
Purity
Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’diylphosphonite
119345-01-6
Antioxidant
0.1
Not given
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
111-03-5
Lubricant
1.0
40%,
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
Glycerol monooleate
- 98 -
Table 3. Formulation details of the PS test material
CAS number
PS
Use
Level (wt %)
Base polymer
97.45
Purity
Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate)
36443-68-2
Antioxidant
0.1
Not given
Tris(nonylphenyl)phosphite
26523-78-4
Antioxidant
0.1
Not given
Di-(2-ethylhexyl) phthalate
117-81-7
Processing
aids/flow promoter
2.0
97+%
N,N-Bis(stearoyl) ethylenediamide
110-30-5
Mould release
agent
0.1
Not given
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
CAS number
PET
Use
Level (wt %)
Base polymer
97.749
Purity
2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
70321-86-7
UV stabilizer
0.25
Not given
Hexanedioic acid polymer with 1,3-benzenedimethanamine
25718-70-1
Acetaldehyde
scavenger
2.0
Not given
147-14-8
Colourant
0.001
97%
Copper phthalocyanine blue
- 99 -
Table 5. Formulation details of the PVC test material
CAS number
PVC
Use
Level (wt %)
Base polymer
62.2
Purity
Dioctyltin bis(ethylmaleate)
68109-88-6
Stabilisers
1.0
> 50%
Dioctyltin bis(2-ethylhexyl thioglycolate)
15571-58-1
Stabilisers
1.0
> 50%
Stabiliser
5.0
Not given
Epoxidised soya bean oil
Stearic acid
57-11-4
Emulsifier
0.3
>97%
Acetyl tributyl citrate
77-90-7
Plasticiser
30.0
98+%
8002-74-2
Lubricant
0.5
Not given
CAS number
Use
Level (wt %)
Purity
Base polymer
94.9
14807-96-6
Mineral filler
5.0
Not given
557-05-1
Mould release
agent
0.1
Not given
Paraffin wax
Table 6. Formulation details of the PA test material
PA
Talc
Zinc stearate
- 100 -
Table 7. List of compounds identified in virgin HDPE
Compounds identified in HDPE
Aromatic hydrocarbons *
Ethylbenzene
o-Xylene
m-Xylene
p-Xylene
Aliphatic hydrocarbons
Undecane
Hexadecane
Heptadecane
Octadecane
Branched alkane 1
Tetracosane
Branched alkane 2
Branched alkane 3
Branched alkenes
1-Octadecene
1-Nonadecene
5-Eicosene
Ketones
6-Dodecanone
2-Nonadecanone
* Proposed, by the authors, to be due to breakdown products of the additives present in
the polymers
Table 8. Organo-tin compounds present in a commercial PVC foil by
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 -
119
Sn Mössbauer
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
Polymer/additive
Molecular formula
Proposed impurities/reaction/breakdown products
Molecular
weight
(g/mol)
Polypropylene
alkanes
-
-
alkenes
-
-
alcohols
-
-
2-methylpropan-1-ol
C4H10O
74
2,4-dimethylpentan-1-ol
C7H16O
116
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(2,4di-tert-butylphenyl)phosphite)
C42H63PO4
663
C14H22O
206
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
C6H6
78
Diparamethyldibenzylidene sorbitol
2,4-di-tert-butylphenol
1,3-di-tert-butyl-benzene
benzene
- 103 -
Table 10 continued. Proposed impurities/reaction/breakdown products for the additives
used in the manufacture of the PP test material
Polymer/additive
Molecular formula
Proposed impurities/reaction/breakdown products
Pentaerythritol tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
Molecular
weight
(g/mol)
C73H108O12
1177
2,6-di-tert-butylbenzoquinone,
2,6-di-tertbutyl-2,5-cyclohexadiene-1,4-dione
C14H20O2
220
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-diene1,5-bis-tert-butyl-6-on-4-(2-carboxy-ethylidene)
C17H24O3
276
C14H22
190
quinone methide methyl ester, cyclohexa-1,4-diene1,5-bis-tert-butyl-6-on-4-(2-carboxy-ethylidene) methyl
ester
C18H26O3
290
tert-butyl-phenol
C10H14O
150
phenol
C6H6O
94
di-isopropyl-benzene
C12H18
162
(C35H68N8)n
Typically
2000
2,2,6,6-tetramethyl-4-piperidinone
C9H17NO
155
2,2,6,6-tetramethyl-4-piperidinol
C9H19NO
157
C9H17N
139
C10H21NO
171
1,3-di-tert-butyl-benzene
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6tetramethyl-4-piperidinyl)imino]],
aza-2,2,6,6-tetramethyl-3-cyclohexene
2,2,6,6-tetramethyl-piperidine methyl ether
- 104 -
Table 10 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the PP test material
Polymer/additive
Molecular formula
Proposed impurities/reaction/breakdown products
Molecular
weight
(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
C8H10
106
2,7,7-trimethyl-5-cycloheptene
C9H17N
139
2,2,6,6-tetramethyl-4-aminopiperidine
C9H20N2
156
(C15H25O4N)n
Typically
3500
1-aza-2,2,6,6-tetramethyl-3-cyclohexeneethanol
C11H21NO
183
methyl-1-aza-2,2,6,6-tetramethyl-3-cyclohexeneethyl
succinate
C16H27NO4
297
aza-1,2,2,6,6-pentamethyl-3-cyclohexene
C10H19N
153
4-hydroxy-1,2,2,6,6-pentamethylpiperidine
C10H21NO
171
C9H17N
139
trans-2,6-dimethyl-2,4,6-heptatriene
C9H14
122
2-methyl-2,4-pentadiene
C6H10
82
C9H19NO
157
butanedioic acid
C4H6O4
118
cis-butanedioic anhydride
C4H4O3
100
C22H43NO
337
C22H41N
319
C22H41O2
339
C9H18O
124
13-oxo-tridecanoic acid amide
C13H25NO
211
13-hydroxy-cis-14-docosenamide
C22H43NO2
353
2,6-dimethylbenzene
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidene
ethanol-alt-1,4-butanedioic acid)
aza-2,2,6,6-tetramethyl-3-cyclohexene
4-hydroxy-2,2,6,6-tetramethylpiperidine
Erucamide
erucyl nitrile
erucic acid, docosenoic acid
nonanal
- 105 -
Table 10 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the PP test material
Polymer/additive
Molecular formula
Proposed impurities/reaction/breakdown products
Glycerol monostearate
Molecular
weight
(g/mol)
C21H42O4
358
octadecanoic acid
C18H36O2
284
tetradecanoic acid
C14H28O2
228
hexadecanoic acid
C16H32O2
256
ethyl stearate
C20H40O2
313
C3H8O
92
glycerol distearate
C39H76O5
624
glycerol tristearate
C57H110O6
890
CaCO3
100
CaO
56
CaC2H2O6
162
glycerol
Calcium carbonate
calcium oxide
calcium hydrogen carbonate
- 106 -
Table 11. Proposed impurities/reaction products/breakdown products for the additives
used in the manufacture of the HDPE test material
Molecular formula
Molecular
weight
(g/mol)
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
C12H12O4P2
282
C26H32O4P2
470
Polymer/additive
Proposed impurities/reaction/breakdown products
HDPE
alkanes
alkenes
ketones
Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’diylphosphonite
R
O
O
P
O
R
P
H
O
R
R
R
R
R = tert-butyl
O
H
P
O
O
P
H
O
R
R
R
R
R = tert-butyl
- 107 -
Table 11 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the HDPE test material
Polymer/additive
Proposed impurities/reaction/breakdown products
O
H
P
Molecular formula
Molecular
weight
(g/mol)
C40H52O4P2
658
C54H72O4P2
846
C68H92O5P2
1051
O
P
HO
H
O
R
R
R = tert-butyl
O
H
P
O
P
HO
H
OH
R = tert-butyl
R
R
R
O
O
P
O
P
O
O
R
R
R
R
R = tert-butyl
- 108 -
Table 11 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the HDPE test material
Molecular formula
Molecular
weight
(g/mol)
C68H92O6P2
1067
PCl3
136
C12H10Cl
C12H9Cl2
C12H8Cl3
C12H7Cl4
C12H6Cl5
C12H5Cl6
C12H4Cl7
C12H3Cl8
C12H2Cl9
C12HCl10
C12Cl11
189
223
257
291
325
359
383
427
461
495
529
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
C4H8
56
Polymer/additive
Proposed impurities/reaction/breakdown products
R
R
R
O
O
P
O
O
P
O
O
R
R
R
R
R = tert-butyl
phosphorus trichloride
polychlorinated biphenyls
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate
t-butylene
- 109 -
Table 11 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the HDPE test material
Molecular formula
Molecular
weight
(g/mol)
C27H46O3
418
C31H54O3
474
thermal oxidation product 1 minus octadecanol
C13H18O3
222
thermal oxidation product 2 minus octadecanol
C9H10O3
166
C18H35NO
281
oleic acid
C18H34O2
282
formamide
CH3NO
45
acetamide
C2H5NO
59
urea
CH4N2O
60
acetyl urea
C3H6N2O2
102
oleyol chloride
C18H33OCl
300
H3N
17
C19H36O2
296
C18H39NO3
317
Polymer/additive
Proposed impurities/reaction/breakdown products
OH
H37C18
O
O
= thermal oxidation product 1
OH
t-Bu
H37C18
O
O
= thermal oxidation product 2
Oleamide
ammonia
methyl oleate
dihydroxy oleamide
- 110 -
Table 11 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the HDPE test material
Molecular formula
Molecular
weight
(g/mol)
O2Ti
80
C13
C17H37NO2
287
C14
C18H39NO2
301
C15
C19H41NO2
315
C2H4O
44
primary amine C13
C13H29N
199
primary amine C14
C14H31N
213
primary amine C15
C15H33N
227
secondary amine C13
C15H33NO
243
secondary amine C14
C16H35NO
257
secondary amine C15
C17H37NO
271
C21H40O4
356
C3H8O3
92
H3O4P
98
oleic acid
C18H34O2
282
dihydroxy oleic acid
C18H41O4
321
C10
C10H21O4SNa
260
C11
C11H23O4SNa
274
C12
C12H25O4SNa
288
C13
C13H27O4SNa
302
C14
C14H29O4SNa
316
C15
C15H31O4SNa
330
C16
C16H33O4SNa
344
C17
C17H35O4SNa
358
Polymer/additive
Proposed impurities/reaction/breakdown products
Titanium dioxide
N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine
ethylene oxide
Glycerol monooleate
glycerol
phosphoric acid
Sodium (C10-C18) alkyl sulfonate
- 111 -
Table 11 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the HDPE test material
Molecular formula
Molecular
weight
(g/mol)
C18H37O4SNa
372
C10 sulphonic acid
C10H23O3S
223
C11 sulphonic acid
C11H25O3S
237
C12 sulphonic acid
C12H27O3S
251
C13 sulphonic acid
C13H29O3S
265
C14 sulphonic acid
C14H31O3S
279
C15 sulphonic acid
C15H33O3S
293
C16 sulphonic acid
C16H35O3S
307
C17 sulphonic acid
C17H37O3S
321
C18 sulphonic acid
C18H39O3S
335
C26H26N2O2S
430
Polymer/additive
Proposed impurities/reaction/breakdown products
C18
2,5-Bis(5'-tert.butylbenzoxazol-2-yl)thiophene
- 112 -
Table 12. Proposed impurities/reaction products/breakdown products for the additives
used in the manufacture of the PS test material
Molecular formula
Molecular
weight
(g/mol)
C8H8
104
styrene dimer
C16H17
209
alpha-methylstyrene
C9H10
118
styrene trimer
C24H25
313
-
-
C4H6
54
-
-
1-phenylethanol
C8H10O
122
acetophenone
C8H8O
120
benzaldehyde
C7H6O
106
phenol
C6H6O
94
ethylbenzene
C8H10
106.
C34H50O8
587
2-tert-butyl-6-methyl-benzoquinone
C11H14O2
178
2-tert-butyl-6-methyl-phenol
C11H16O
164
C6H6O
94
C10H14O
150
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)-2,5cyclohexadiene-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
Polymer/additive
Proposed impurities/reaction/breakdown products
Polystyrene (HIPS)
styrene
styrene oligomers
butadiene
butadiene oligomers
Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4hydroxy-m-tolyl)-propionate)
phenol
tert-butyl-phenol
methylphenol
- 113 -
Table 12 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the PS test material
Molecular formula
Molecular
weight
(g/mol)
C45H69O3P
689
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
C24H38O4
391
C16H23O4
279
2-ethylhexanol
C8H18O
130
octanol
C8H18O
130
C10H10O4
178
2-ethylhexyl aldehyde
C8H17O
129
2-ethylhexanoic acid
C8H16O2
144
phthalic acid
C8H6O4
166
C38H76N2O2
593
octadecanoic acid
C18H36O2
285
octadecanol
C18H38O
271
C18H37ON
284
Polymer/additive
Proposed impurities/reaction/breakdown products
TNPP
nonylphenol
DEHP
MEHP
dimethylphthalate
N,N-Bis(stearoyl)ethylenediamide
octadecanamide
Polyethylene glycol 4-tert-octyl-phenyl ether, n~5
and Polyethylene glycol 4-tert-octyl-phenyl ether,
n=9-10
octylphenol
octylphenol ethoxylates oligomers
- 114 -
426-646
C14H22O
206
-
-
Table 12 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the PS test material
Polymer/additive
Proposed impurities/reaction/breakdown products
2-(2’-Hydroxy-5’-methylphenyl)benzotriazole
benzotriazole
- 115 -
Molecular formula
Molecular
weight
(g/mol)
C13H11N3O
225
C6H5N3
119
Table 13. Proposed impurities/reaction products/breakdown products for the additives
used in the manufacture of the PET test material
Molecular formula
Molecular
weight
(g/mol)
dimethyl terephthalate
C10H10O4
194
methyl vinyl terephthalate
C11H10O4
206
ethylene glycol
C2H6O2
62
benzoic acid
C7H6O2
122
vinyl benzoate
C9H8O2
148
acetophenone
C8H8O
120
C16H14O4
270
C3H6O
58
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
-
-
C30H29N3O
448
C6H5N3
119
Polymer/additive
Proposed impurities/reaction/breakdown products
Polyethylene terephthalate
ethylene dibenzoate
propionaldehyde
benzene
2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1phenylethyl)phenol
benzotriazole
- 116 -
Table 13 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the PET test material
Molecular formula
Molecular
weight
(g/mol)
-
-
hexanedioic acid
C6H10O4
146
1,3-benzenedimethanamine
C8H12N2
136
C5H8O
84
C10H16O
152
C7H9N
107
C32H16CuN8
576
phthalodinitrile
C8H4N2
128
benzonitrile
C7H5N
103
HCN
27
Polymer/additive
Proposed impurities/reaction/breakdown products
Hexanedioic acid polymer with 1,3benzenedimethanamine
cyclopentanone
2-cyclopentylcyclopentanone
aminotoluene
Copper phthalocyanine blue
hydrogen cyanide
- 117 -
Table 14. Proposed impurities/reaction products/breakdown products for the additives
used in the manufacture of the PVC test material
Molecular formula
Molecular
weight
(g/mol)
C2H3Cl
62
C6H6
78
aromatic hydrocarbons
-
-
PVC oligomers
-
-
C28H48O8Sn
631
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
C36H72O4S2Sn
751
C10H20O2S
204
C2H4O2S
92
C8H18O
130
n-octyltin-tris(ethylhexylthioglycolate)
C38H74O6S3Sn
841
di-n-octyltin-(ethylhexylthioglycolate) chloride
C26H53O2SSn
548
n-octyltin-bis(ethylhexylthioglycolate) chloride
C28H55O4S2Sn
Cl
678
Polymer/additive
Proposed impurities/reaction/breakdown products
PVC
vinyl chloride
benzene
Di-n-octyltin-bis(ethylmaleate)
octane
Di-n-octyltin-bis(ethylhexylthioglycolate)
2-ethylhexyl mercaptoacetate
mercaptoacetic acid
2-ethylhexanol
ESBO
linolenic acid
C18H30O2
oleic acid
C18H34O2
282
hydrochlorinated derivatives
-
-
allylic chlorinated ethers
-
-
cyclic degradation products
-
-
- 118 -
Table 14 continued. Proposed impurities/reaction products/breakdown products for the
additives used in the manufacture of the PVC test material
Molecular formula
Molecular
weight
(g/mol)
C18H36O2
284
palmitic acid
C16H32O2
256
octadecanol
C18H38O
270
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
Polymer/additive
Proposed impurities/reaction/breakdown products
Stearic acid
ATBC
Paraffin wax
alkanes
- 119 -
Table 15. Proposed impurities/reaction products/breakdown products for the additives
used in the manufacture of the PA test material
Polymer/additive
Proposed impurities/reaction/breakdown
products
Molecular formula
Molecular
weight
(g/mol)
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
C5H11NO
101
3-(1-methylethyl)-pyridine
C8H11N
121
2-butyl-pyridine
C9H13N
135
C13H27NO
213
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
Mg3SiO12H2
294
Zn(C18H35O2)2
632
C18H36O2
284
Nylon
caprolactam
pentanamide
N,N-hexamethylenebisformamide
2-butyl-cyclopentanone
Talc
Zinc stearate
stearic acid
- 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
ethanol
extract
Detected in
isooctane
extract
Diparamethyldibenzylidene sorbitol
No
No
Tris(2,4-di-tert-butylphenyl)phosphate
Yes
Yes
Pentaerythritol tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
No
No
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]],
Mn ca. 2000
No
No
Poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine
ethanol-alt-1,4-butanedioic acid), Mn ca. 3500
No
No
Erucamide
Yes
Yes
Glycerol monostearate
Yes
No
Calcium carbonate
No
No
Tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’diylphosphonite
*
*
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate
Yes
Yes
Oleamide
Yes
Yes
Titanium dioxide
No
No
#
#
Glycerol monooleate
Yes
Yes
Sodium (C10-C18) alkyl sulfonate
No
No
2,5-Bis(5'-tert.butylbenzoxazol-2-yl)thiophene
Yes
Yes
Ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxym-tolyl)-propionate)
Yes
Yes
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
Additive
PP
HDPE
N,N-Bis-(2-hydroxyethyl)alkyl(C13-C15)amine
PS
- 122 -
Table 17 continued. Solutions of additives in ethanol and isooctane analysed by GCMS
Additive
Detected in
ethanol
extract
Detected in
isooctane
extract
Yes
Yes
2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1phenylethyl)phenol
Yes
Yes
Hexanedioic acid polymer with 1,3benzenedimethanamine
No
No
Copper phthalocyanine blue
No
No
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
Talc
No
No
Zinc stearate
No
No
2-(2'-Hydroxy-5'-methylphenyl)benzotriazole
PET
PVC
PA
* 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
PP1
7.0-10.0
1168
PP2
8.5
8
PP3
9.6
6.6
13
PP4
10.2
7.3
10
Present in/derived from
Predicted
Isooctane
glycerol
Reaction/breakdown product
derived from glycerol
monostearate
Yes
butanedioic acid, dimethyl ester
Reaction/breakdown product
No
25
2-methylbenzaldehyde
Reaction/breakdown product
No
35
unknown
Reaction/breakdown product
No
Yes
PP5
13.9
6
1-aza-2,2,6,6-tetramethyl-3cyclohexeneethanol
Reaction/breakdown product
derived from poly(4-hydroxy2,2,6,6-tetramethyl-1piperidine ethanol-alt-1,4butanedioic acid),
PP6
15.4
16
unknown
Reaction/breakdown product
No
PP7
15.9
85
2,4-di-t-butyl phenol
Present in tris(2,4-di-tertbutylphenyl)phosphite
standard
Yes
PP8
17.3
unknown
Reaction/breakdown product
No
PP9
19.0
10
tetradecanoic acid, ethyl ester
Present in glycerol
monostearate
No
PP10
20.4
20
unknown
Reaction/breakdown product
No
15.1
30
68
- 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
PP11
PP12
20.6
Isooctane
18.5
20.8
Ethanol
Present in/derived from
Predicted
Isooctane
methyl-3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate
Present in pentaerythritol
tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
standard
Yes
21
hexadecanoic acid
Reaction/breakdown product,
ions suggest derived from
glycerol monostearate
Yes
178
ethyl-3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate
Present in pentaerythritol
tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
standard
Yes
88
370
PP13
21.2
PP14
22.8
20.7
33
35
octadecanoic acid
Reaction/breakdown product,
ions suggest derived from
glycerol monostearate
Yes
PP15
23.1
20.9
200
58
octadecanoic acid, ethyl ester-
Present in glycerol
monostearate standard
Yes
unknown
Reaction/breakdown product,
ions suggest derived from
poly(4-hydroxy-2,2,6,6tetramethyl-1-piperidine
ethanol-alt-1,4-butanedioic
acid),
No
PP16
23.2
21.3
4
35
- 125 -
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)
Peak
PP17
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Present in/derived from
Predicted
Ethanol
Isooctane
Ethanol
Isooctane
23.5
21.4
18
80
unknown
Reaction/breakdown product
No
PP18
21.4
55
unknown
Reaction/breakdown product
No
PP19
21.8
53
unknown
Reaction/breakdown product
No
65
unknown
Reaction/breakdown product
No
PP20
24.0
PP21
24.1
65
glycerol monotetradecanoate
Reaction/breakdown product,
ions suggest derived from
glycerol monostearate
No
PP22
24.5
18
unknown
Reaction/breakdown product
No
PP23
24.6
18
oleamide
Present in erucamide
standard
No
PP24
24.6
28
eicosanoic acid, ethyl ester
Present in glycerol
monostearate standard
No
23.1
118
unknown
Reaction/breakdown product
No
23.5
333
unknown
Present in glycerol
monostearate standard
No
glycerol monohexadecanoate
Reaction/breakdown product,
ions suggest derived from
glycerol monostearate
No
PP25
PP26
PP27
25.6
25.8
21.9
25
4698
1578
- 126 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PP28
26.2
20
amide
Present in erucamide
standard
No
PP29
26.5
33
unknown
Reaction/breakdown product
No
PP30
26.9
20
unknown
Reaction/breakdown product
No
PP31
27.0
18
unknown
Present in glycerol
monostearate standard
No
PP32
27.2
unknown
Present in glycerol
monostearate standard
No
PP33
27.4
glycerol monostearate
Glycerol monostearate
Additive
PP34
27.6
erucamide
Erucamide
Additive
PP35
27.9
35
alkyl amide
Present in erucamide
standard
No
PP36
28.0
18
unknown
Reaction/breakdown product
No
methyl-1-aza-2,2,6,6-tetramethyl-3cyclohexeneethyl succinate
Reaction/breakdown product,
ions suggest derived from
poly(4-hydroxy-2,2,6,6tetramethyl-1-piperidine
ethanol-alt-1,4-butanedioic
acid),
Yes
PP37
28.1
24.9
503
1258
9670
25.6
26.0
4
48
33
130
- 127 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PP38
28.8
35
glycerol monoeicosanoate
Reaction/breakdown product,
ions suggest derived from
glycerol monostearate
No
PP39
28.9
13
unknown
Reaction/breakdown product
No
PP40
29.0
50
tetracosenamide
Present in erucamide
standard
No
PP41
29.2
33
unknown
Present in erucamide
standard
No
PP42
29.4
8
unknown
Reaction/breakdown product
No
No
PP43
29.9
27.9
18
25
Reaction/breakdown product,
ions suggest derived from
poly(4-hydroxy-2,2,6,6-tetramethyl-1poly(4-hydroxy-2,2,6,6piperidine ethanol-alt-1,4-butanedioic
tetramethyl-1-piperidine
acid), monomer + piperidinyl ring
ethanol-alt-1,4-butanedioic
acid),
PP44
30.3
28.3
30
90
unknown
Reaction/breakdown product
No
PP45
30.4
unknown
Reaction/breakdown product
No
23
- 128 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
Reaction/breakdown product,
ions suggest derived from
pentaerythritol tetrakis(3,5-ditert-butyl-4hydroxyhydrocinnamate)
No
No
PP46
28.9
25
pentaerythritol tetrakis(3,5-di-tertbutyl-4-hydroxyhydrocinnamate)
related
PP47
29.3
33
unknown
Present in tris(2,4-di-tertbutylphenyl)phosphite
standard
29.5
35
tris(2,4-di-tert-butylphenyl)phosphite
Tris(2,4-di-tertbutylphenyl)phosphite
oxidised tris(2,4-di-tertbutylphenyl)phosphite
Present in tris(2,4-di-tertbutylphenyl)phosphite
standard
Yes
poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4-piperidinyl)imino]-1,6hexanediyl-[(2,2,6,6-tetramethyl-4piperidinyl)imino]], repeating unit
Present in poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4piperidinyl)imino]-1,6hexanediyl-[(2,2,6,6tetramethyl-4piperidinyl)imino]],
No
unknown
Reaction/breakdown product
No
PP48
31.5
PP49
32.9
PP50
34.2
PP51
35.1
55
560
32.0
17885
3
1463
- 129 -
Additive
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
PP52
36.4
5
PP53
36.6
105
PP54
39.1
8
PP55
39.7
178
Present in/derived from
Predicted
Isooctane
unknown
Reaction/breakdown product
No
(degradation product of) diglyceride
Reaction/breakdown product,
ions suggest derived from
glycerol monostearate
No
pentaerythritol tetrakis(3,5-di-tertbutyl-4-hydroxyhydrocinnamate)
related (3 subunits)
Reaction/breakdown product,
ions suggest derived from
pentaerythritol tetrakis(3,5-ditert-butyl-4hydroxyhydrocinnamate)
No
(degradation product of) diglyceride
Reaction/breakdown product,
ions suggest derived from
glycerol monostearate
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
HDPE1
6.0
1
alkane
and
unknown
Reaction/breakdown product
and
Reaction/breakdown product
Yes
and
No
HDPE2
6.6
3
nonanal
Reaction/breakdown product
No
HDPE3
9.2
1
2-methyl-dodecene
Reaction/breakdown product
Yes
Yes
HDPE4
9.3
4
p-t-butylphenol
Reaction/breakdown product
derived from tetrakis(2,4-ditert-butylphenyl)[1,1-biphenyl]4,4’-diylphosphonite
HDPE5
9.4
4
tridecane
Reaction/breakdown product
Yes
Reaction/breakdown product
and
Reaction/breakdown product
Yes
and
No
HDPE6
9.5
2
tetradecene
and
unknown
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
33
2-methoxy-1-octene
Reaction/breakdown product
No
37
2-tridecanone
Reaction/breakdown product
Yes
HDPE10
HDPE11
11.5
11.4
11.7
8
- 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Present in/derived from
Predicted
Ethanol
Isooctane
Ethanol
Isooctane
HDPE12
11.8
12.1
60
138
pentadecane
Present in sodium (C10-C18)
alkyl sulfonate standard
Yes
HDPE13
12.1
12.2
12
458
2,4-bis(1,1-dimethylethyl)phenol
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
Yes
HDPE14
12.2
43
tridecanal
Reaction/breakdown product
No
HDPE15
13.7
4
unknown
Reaction/breakdown product
No
HDPE16
13.8
6
unknown
Reaction/breakdown product
No
HDPE17
14.0
9
unknown
Reaction/breakdown product
No
HDPE18
13.9
14.1
4
17
dodecanone
Reaction/breakdown product
Yes
HDPE19
14.2
14.4
72
182
heptadecane
Present in sodium (C10-C18)
alkyl sulfonate standard
Yes
14
tridecyloxirane
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
No
HDPE20
HDPE21
HDPE22
14.6
15.0
10
15.8
1
- 132 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
HDPE23
Isooctane
15.9
HDPE24
Ethanol
4
pentadecanoic acid, ethyl ester
Reaction/breakdown product,
ions suggest related to
glycerol monooleate
No
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
No
pentadecanitrile
HDPE25
16.3
16.5
4
Predicted
Isooctane
6
16.1
Present in/derived from
11
and
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
and
Reaction/breakdown product
No
and
No
Present in octadecyl 3,5-di-tbutyl-4hydroxyhydrocinnamate
standard
No
HDPE26
16.8
21
methyl-3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate
HDPE27
17.9
3
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
No
heptadecanoic acid, ethyl ester
Present in glycerol
monooleate standard
No
HDPE28
17.9
16
- 133 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
HDPE29
Isooctane
17.9
Ethanol
28
18.0
Predicted
Isooctane
octadecenoic acid, methyl ester
unknown
HDPE30
Present in/derived from
12
and
unknown
Reaction/breakdown product,
ions suggest derived from
glycerol monooleate
No
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
and
Reaction/breakdown product
and
No
Present in oleamide
and
Reaction/breakdown product
No
and
No
No
HDPE31
18.0
4
pentadecanamide
and
unknown
HDPE32
18.1
44
hexadecanedioic acid
Reaction/breakdown product
No
HDPE33
18.2
25
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
No
- 134 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
18.1
18.3
7
Predicted
Isooctane
unknown
HDPE34
Present in/derived from
41
and
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
and
Present in oleamide standard
and
No
No
HDPE35
18.3
30
unknown
Reaction/breakdown product
No
HDPE36
18.4
23
1-hexadecanol
Reaction/breakdown product
No
19
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
No
95
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
No
HDPE37
HDPE38
18.5
18.6
18.8
17
HDPE39
18.9
79
unknown
Reaction/breakdown product
No
HDPE40
19.1
9
octadecenoic acid
Reaction/breakdown product,
ions suggest derived from
oleamide
Yes
- 135 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
HDPE42
18.9
19.0
HDPE43
HDPE44
19.3
461
48
19.4
19.3
HDPE45
HDPE46
19.2
and
hexadecenamide
Reaction/breakdown product,
ions suggest derived from
glycerol monooleate
and
Present in oleamide standard
23
hexadecanamide
Present in oleamide standard
No
405
docosane
Reaction/breakdown product
Yes
1-docosene
Reaction/breakdown product
Yes
unknown
Reaction/breakdown product
No
32
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
19.4
No
721
4
19.6
19.7
13
13
Predicted
Isooctane
methyl oleate
HDPE41
Present in/derived from
Yes
and
No
HDPE47
19.8
82
unknown
Reaction/breakdown product,
ions suggest derived from
glycerol monooleate
No
HDPE48
19.8
38
unknown
Reaction/breakdown product
No
HDPE49
19.9
125
unknown
Reaction/breakdown product
No
HDPE50
20.0
102
unknown
Reaction/breakdown product
No
- 136 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
HDPE51
Isooctane
Ethanol
20.2
HDPE52
HDPE53
20.6
HDPE54
20.6
unknown
Reaction/breakdown product
No
unknown
Present in N,N-bis-(2hydroxyethyl)alkyl(C13C15)amine standard
No
oleamide
Oleamide standard
Additive
1267
oleamide
Oleamide standard
Additive
20
429
21.0
432
Predicted
Isooctane
7
20.6
Present in/derived from
HDPE55
21.1
581
tetracosane
Reaction/breakdown product
HDPE56
21.4
1020
glycerol monooleate
Glycerol monooleate standard Additive
HDPE57
21.6
4
unknown
Reaction/breakdown product
No
HDPE58
21.7
6
unknown
Reaction/breakdown product
No
HDPE59
21.8
10
unknown
Reaction/breakdown product
No
HDPE60
21.9
10
unknown
Reaction/breakdown product
No
HDPE61
21.9
12
unknown
Reaction/breakdown product
No
HDPE62
22.3
2
unknown
Reaction/breakdown product
No
HDPE63
23.0
15
unknown
Present in glycerol
monooleate standard
No
- 137 -
Yes
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
unknown
Reaction/breakdown product,
ions suggest derived from
glycerol monooleate
No
HDPE64
23.5
387
HDPE65
24.6
2
cholesta-2,4-diene
Reaction/breakdown product,
ions suggest derived from
glycerol monooleate
No
11
cholesta-3,5-diene
Present in glycerol
monooleate standard
No
2
unknown
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
No
No
HDPE66
HDPE67
24.6
24.9
26.0
19
HDPE68
26.6
1
unknown
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
HDPE69
27.0
2
unknown
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
No
HDPE70
27.7
2
unknown
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
No
- 138 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
HDPE71
27.9
3
unknown
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
HDPE72
28.2
4
unknown
Reaction/breakdown product
No
HDPE73
28.9
2
unknown
Reaction/breakdown product
No
666
octadecyl 3,5-di-t-butyl-4hydroxyhydrocinnamate
Octadecyl 3,5-di-t-butyl-4hydroxyhydrocinnamate
standard
HDPE74
29.4
29.8
331
No
Additive
HDPE75
30.0
22
unknown
Reaction/breakdown product
No
HDPE76
30.4
5
unknown
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
No
HDPE77
30.6
3
unknown
Reaction/breakdown product
No
HDPE78
30.7
4
unknown
Reaction/breakdown product
No
HDPE79
30.9
11
unknown
Reaction/breakdown product
No
HDPE80
31.8
32
unknown
Present in tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]4,4’-diylphosphonite standard
No
- 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
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
branched alkane
Reaction/breakdown product
No
PS4
15.9
benzothiophene related
Reaction/breakdown product
No
PS5
18.0
16.0
5
3
unknown
Present in TNPP standard
No
PS6
18.1
16.1
3
5
unknown
Present in TNPP standard
No
PS7
18.2
16.2
25
20
unknown
Present in TNPP standard
No
PS8
18.3
16.3
48
8
unknown
Present in TNPP standard
No
PS9
18.4
16.4
8
10
unknown
Present in TNPP standard
No
PS10
18.5
16.5
10
13
unknown
Present in TNPP standard
No
PS11
18.6
16.6
13
5
unknown
Present in TNPP standard
No
PS12
18.7
16.7
2
8
unknown
Present in TNPP standard
No
PS13
19.1
1
unknown
Present in TNPP standard
No
2
3-methyl-5-tert-butyl-4hydroxyphenyl methylpropanoate
Present in
ethylenebis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-mtolyl)-propionate) standard
Yes
PS14
19.6
13.6
1
5
3
17.6
1
- 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
PS15
20.3
PS16
21.9
PS17
Isooctane
Ethanol
1
20.6
Predicted
Isooctane
Present in
3-methyl-5-tert-butyl-4-hydroxyphenyl ethylenebis(oxyethylene)bisethylpropanoate
(3-(5-tert-butyl-4-hydroxy-mtolyl)-propionate) standard
1
19.9
Present in/derived from
Yes
2
2-(2’-hydroxy-5’methylphenyl)benzotriazole
2-(2’-Hydroxy-5’methylphenyl)benzotriazole
4
2-(2-4(1,1,3,3tetramethylbutyl)phenoxy)ethoxy)
ethanol
Present in polyethylene glycol
4-tert-octyl-phenyl ether, n=910 standard
No
No
Additive
PS18
25.4
23.5
20
80
isomer of DEHP
Present in DEHP standard
PS19
25.7
23.7
5
22
DEHP
DEHP
Additive
PS20
39.9
38.0
1
3
ethylenebis(oxyethylene)bis-(3-(5tert-butyl-4-hydroxy-m-tolyl)propionate)
Ethylenebis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-mtolyl)-propionate)
Additive
- 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PET1
26.2
43
unknown
Reaction/breakdown product
derived from copper
phthalocyanin blue
No
PET2
32.9
75
2-(2H-benzotriazole-2-yl)-4,6-bis(1methyl-1-phenylethyl)phenol
2-(2H-Benzotriazole-2-yl)-4,6bis(1-methyl-1phenylethyl)phenol
Additive
- 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
PVC1
3.9
3886
PVC2
4.2
60
Present in/derived from
Predicted
Isooctane
acetic acid, mercapto-, ethyl ester
Reaction/breakdown product
No
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
9136
2-ethyl-1-hexanol
Present in dioctyltin bis(2ethylhexyl thioglycolate)
standard
No
di-2-ethylhexyl chloroformate
Reaction/breakdown product
No
PVC8
5.5
5.6
73351
PVC9
6.2
156
PVC10
6.5
8
unknown
Present in dioctyltin
bis(ethylmaleate) standard
No
PVC11
6.5
10
alkane
Reaction/breakdown product
No
PVC12
6.6
16
nonanal
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
1-octanethiol
Reaction/breakdown product
No
PVC13
PVC14
6.6
74
7.0
5
- 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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Isooctane
PVC15
7.0
7.2
191
666
PVC16
7.3
PVC17
7.4
7.6
13
2345
PVC18
7.5
7.7
108
PVC19
7.6
7.8
49
PVC20
Predicted
2-ethylhexyl acetate
Present in dioctyltin bis(2ethylhexyl thioglycolate)
standard
No
unknown
Reaction/breakdown product
No
2-butenedioic acid (Z)-, diethyl ester
Present in dioctyltin
bis(ethylmaleate) standard
No
6
carbonic acid dibutyl ester
Reaction/breakdown product
No
56
2-butenedioic acid (E)-, diethyl ester
Present in dioctyltin
bis(ethylmaleate) standard
No
3
3-dodecene (E)
Reaction/breakdown product
No
292
7.9
Present in/derived from
PVC21
7.7
30
unknown
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
PVC25
8.1
18
unknown
Reaction/breakdown product
No
PVC26
8.2
81
unknown
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
PVC27
8.5
4
- 144 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
PVC28
Isooctane
8.5
Ethanol
Present in/derived from
Predicted
Isooctane
141
unknown
Reaction/breakdown product
No
PVC29
8.8
7
pentanoic acid,4-oxo-,butyl ester
Reaction/breakdown product
No
PVC30
8.9
8
butanedioic acid, hydroxy-, diethyl
ester
Reaction/breakdown product
No
PVC31
9.0
1
1,1'-oxybishexane
Reaction/breakdown product
No
PVC32
9.1
28
unknown
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
PVC33
8.9
76
PVC34
9.3
4
unknown
Reaction/breakdown product
No
PVC35
9.4
9
tridecane
Reaction/breakdown product
No
6
unknown
Reaction/breakdown product
No
PVC36
9.2
9.5
210
PVC37
9.6
84
unknown
Reaction/breakdown product
No
PVC38
9.7
37
unknown
Reaction/breakdown product
No
28
ethyl 3,3-diethoxypropionate
Present in dioctyltin
bis(ethylmaleate) standard
No
unknown
Reaction/breakdown product
No
2-butenedioic acid (Z)-, diethyl ester
Reaction/breakdown product
No
PVC39
9.5
PVC40
9.8
PVC41
9.8
89
30
10.1
8
- 145 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
PVC42
Isooctane
Ethanol
10.2
Present in/derived from
Predicted
Isooctane
69
chloroacetic acid, 2-ethylhexyl ester
Reaction/breakdown product
No
PVC43
10.0
443
unknown
Reaction/breakdown product
No
PVC44
10.3
95
unknown
Reaction/breakdown product
No
PVC45
10.6
6
unknown
Reaction/breakdown product
No
PVC46
10.7
10
1-tetradecene
Reaction/breakdown product
No
PVC47
10.7
585
unknown
Reaction/breakdown product
No
PVC48
10.7
214
unknown
Reaction/breakdown product
No
PVC49
10.8
151
unknown
Reaction/breakdown product
No
PVC50
11.0
70
2,6-(1,1-dimethylethyl)phenol
Reaction/breakdown product
No
5891
isooctyl mercaptoacetate
Present in dioctyltin bis(2ethylhexyl thioglycolate)
standard
Yes
6026
butylated hydroxytoluene
Present in dioctyltin
bis(ethylmaleate) standard
No
PVC51
11.2
PVC52
11.9
12.2
20380
PVC53
12.1
141
8-hexyl pentadecane
Present in dioctyltin
bis(ethylmaleate) standard
No
PVC54
12.2
50
unknown
Reaction/breakdown product
No
- 146 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PVC55
12.3
12.6
142
302
7-methyl pentadecane
Present in dioctyltin
bis(ethylmaleate) and
dioctyltin bis(2-ethylhexyl
thioglycolate) standards
PVC56
12.5
12.8
192
317
7-methyl-octandecan-7-ol
Present in dioctyltin bis(2ethylhexyl thioglycolate)
standard
No
57
hexadecene
Reaction/breakdown product
No
441
diethyl toluamide
Reaction/breakdown product
No
2-butenedioic acid (Z)-, diethyl ester
Reaction/breakdown product
No
PVC57
13.1
PVC58
12.7
PVC59
12.8
345
PVC60
12.9
10971
dibutyl itaconate
Reaction/breakdown product
No
PVC61
13.0
2435
unknown
Reaction/breakdown product
No
hexadecane
Present in dioctyltin
bis(ethylmaleate) and
dioctyltin bis(2-ethylhexyl
thioglycolate) standards
No
PVC62
13.2
69
No
13.3
4450
PVC63
13.3
84
unknown
Reaction/breakdown product
No
PVC64
13.3
295
unknown
Reaction/breakdown product
No
PVC65
13.4
92
unknown
Reaction/breakdown product
No
- 147 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PVC66
13.7
679
unknown
Reaction/breakdown product
No
PVC67
13.7
65
ethyl citrate
Reaction/breakdown product
No
1,1'-oxybisoctane
Present in dioctyltin
bis(ethylmaleate) and
dioctyltin bis(2-ethylhexyl
thioglycolate) standards
No
unknown
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
PVC68
13.7
14.0
5255
9248
PVC69
13.8
PVC70
13.9
PVC71
14.0
104
unknown
Reaction/breakdown product
No
PVC72
14.2
309
unknown
Reaction/breakdown product
No
38
14.2
286
42
PVC73
14.6
33
p-toluenesulfonic acid, n-hexyl ester
Reaction/breakdown product
No
PVC74
14.7
22
unknown
Reaction/breakdown product
No
PVC75
14.8
20
o-acetylcitric acid triethyl ester
Reaction/breakdown product
No
benzenesulfonic acid, 4-methyl-, butyl
Reaction/breakdown product
ester
No
unknown
No
PVC76
14.6
PVC77
14.8
14.9
1042
553
1033
- 148 -
Reaction/breakdown product
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
PVC78
Isooctane
Ethanol
15.1
Present in/derived from
Predicted
Isooctane
4367
benzenesulfonic acid, 4-methyl-,
butylester
Reaction/breakdown product
No
PVC79
15.2
525
unknown
Reaction/breakdown product
No
PVC80
15.2
4130
unknown
Reaction/breakdown product
No
PVC81
15.3
2195
unknown
Reaction/breakdown product
No
PVC82
15.4
7028
unknown
Reaction/breakdown product
No
nonadecane
Reaction/breakdown product
No
o-acetylcitric acid, triethyl ester
Present in ATBC standard
No
unknown
Reaction/breakdown product
No
unknown
and
unknown
Present in ESBO standard
and
Present in ATBC standard
No
196
hexadecanoic acid, ethyl ester
Reaction/breakdown product
No
706
unknown
Present in ATBC standard
No
1-propene-1,2,3-tricarboxylic acid,
tributyl ester
Present in ATBC standard
No
ATBC
ATBC
PVC83
PVC84
16.5
16.3
PVC85
PVC86
17.2
75
204156
17.4
18.1
PVC89
PVC90
8518
16.9
PVC87
PVC88
56
18.3
134061
19.0
19.2-19.8
19.9
269205
- 149 -
Additive
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PVC91
20.2
1202
unknown
Reaction/breakdown product
No
PVC92
20.3
202
unknown
Reaction/breakdown product
No
PVC93
20.3
243
butyl citrate
Present in ATBC standard
Yes
PVC94
20.4
347
unknown
Present in ATBC standard
No
PVC95
20.5
1145
unknown
Reaction/breakdown product
No
PVC96
20.5
861
unknown
Present in ESBO standard
No
PVC97
20.7
111135
unknown
Reaction/breakdown product
No
PVC98
20.8
1419
octadecanoic acid, butyl ester
Reaction/breakdown product
No
PVC99
21.1
45
unknown
Reaction/breakdown product
No
PVC100
21.2
916
unknown
Reaction/breakdown product
No
PVC101
20.9
4171
unknown
Reaction/breakdown product
No
PVC102
21.1
10767
unknown
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
butyl citrate
Present in ATBC standard
No
unknown
Present in ATBC standard
No
PVC103
PVC104
21.4
21.1
PVC105
PVC106
68
328
21.4
21.2
158
161
- 150 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PVC107
21.5
188
unknown
Reaction/breakdown product
No
PVC108
21.5
82
unknown
Present in ATBC standard
No
tetracosane
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
PVC109
21.4
PVC110
538
21.7
428
PVC111
21.4
447
unknown
Reaction/breakdown product
No
PVC112
21.5
119
unknown
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
PVC113
PVC114
21.8
21.8
454
108180
PVC115
22.2
350
unknown
Reaction/breakdown product
No
PVC116
22.2
237
di-2-ethylhexyl phthalate
Reaction/breakdown product
No
PVC117
23.0
673
unknown
Present in dioctyltin bis(2ethylhexyl thioglycolate)
standard
No
PVC118
23.0
41
unknown
Reaction/breakdown product
No
PVC119
22.8
1724
unknown
Reaction/breakdown product
No
PVC120
22.9
226
hexadecanoic acid,2,3bis(acetyloxy)propyl ester
Reaction/breakdown product
No
- 151 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PVC121
23.4
389
diisononyl phthalate
Reaction/breakdown product
No
PVC122
23.5
543
diisononyl phthalate
Reaction/breakdown product
No
PVC123
23.7
460
diisononyl phthalate
Reaction/breakdown product
No
PVC124
23.9
1103
diisononyl phthalate
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
PVC125
24.2
40
PVC126
24.0
518
diisononyl phthalate
Reaction/breakdown product
No
PVC127
24.1
550
unknown
Reaction/breakdown product
No
PVC128
24.1
1070
diisononyl phthalate
Reaction/breakdown product
No
PVC129
24.2
123
diisononyl phthalate
Reaction/breakdown product
No
PVC130
24.3
1942
diisononyl phthalate
Reaction/breakdown product
No
unknown
Reaction/breakdown product
No
PVC131
25.6
65
PVC132
25.5
340
unknown
Reaction/breakdown product
No
PVC133
26.1
217
unknown
Reaction/breakdown product
No
PVC134
26.7
772
unknown
Reaction/breakdown product
No
PVC135
26.7
931
unknown
Reaction/breakdown product
No
PVC136
26.7
1358
unknown
Reaction/breakdown product
No
- 152 -
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)
Peak
Average
Average
tr
tr
concentration concentration Proposed identity
(minutes) (minutes)
(µg/dm2)
(µg/dm2)
Ethanol
Isooctane
Ethanol
Present in/derived from
Predicted
Isooctane
PVC137
26.9
88
unknown
Reaction/breakdown product
No
PVC138
27.0
161
unknown
Reaction/breakdown product
No
PVC139
27.4
4908
unknown
Reaction/breakdown product
No
PVC140
27.5
26525
unknown
Reaction/breakdown product
No
PVC141
27.6
6510
unknown
Reaction/breakdown product
No
PVC142
27.9
678
unknown
Reaction/breakdown product
No
PVC143
29.4
129
unknown
Reaction/breakdown product
No
202
unknown
Reaction/breakdown product
No
PVC144
29.8
30.7
573
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
Peak
tr (minutes)
1st dimension
tr (minutes)
2nd dimension
X1
14.1
X2
X3
Proposed identity
Derived from
Predicted
1.19
unknown
Reaction/breakdown product
No
16.1
1.17
unknown
Reaction/breakdown product
No
16.1
1.48
2,6-dimethyl-2,5-heptadieen-4-one
Reaction/breakdown product
No
Yes
X4
16.3
1.40
2,2,6,6-tetramethyl-4-piperidinamine
Derived from poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4-piperidinyl)imino]1,6-hexanediyl-[(2,2,6,6tetramethyl-4-piperidinyl)imino]],
X5
16.5
1.52
3,5,5-trimethyl-cyclohexen-1-one
Reaction/breakdown product
No
unknown
Derived from poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4-piperidinyl)imino]1,6-hexanediyl-[(2,2,6,6tetramethyl-4-piperidinyl)imino]],
No
Yes
X6
16.7
1.35
X7
17.1
1.47
2,2,6,6-tetramethyl-4-piperidinol
Derived from poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4-piperidinyl)imino]1,6-hexanediyl-[(2,2,6,6tetramethyl-4-piperidinyl)imino]],
X8
18.0
1.10
unknown
Reaction/breakdown product
No
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
Peak
tr (minutes)
1st dimension
tr (minutes)
2nd dimension
X10
27.6
X11
29.1
Proposed identity
Derived from
Predicted
1.37
unknown
Reaction/breakdown product
No
1.82
quinine methide related
Derived from pentaerythritol
tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
No
No
X12
29.5
1.64
unknown
Derived from poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4-piperidinyl)imino]1,6-hexanediyl-[(2,2,6,6tetramethyl-4-piperidinyl)imino]],
X13
29.9
1.73
3,5-di-tert-butyl-4-hydroxybenzaldehyde
Derived from pentaerythritol
tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
Yes
X14
30.7
1.74
3,5-di-tert-butyl-4-hydroxyacetophenone
Derived from pentaerythritol
tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
Yes
X15
32.5
1.33
hexadecanoic acid, methyl ester
Derived from glycerol
monostearate
No
X16
35.6
1.36
octadecanoic acid, methyl ester
Derived from glycerol
monostearate
No
X17
36.5
2.75
4,4’-(1-methylethylidene)bisphenol
Reaction/breakdown product
No
X18
36.6
1.42
eicosanoic acid, methyl ester
Derived from glycerol
monostearate
No
- 155 -
Table 23 continued. Additional peaks observed in the concentrated ethanol extracts of PP + additives with GCxGC-TOF-MS
Peak
tr (minutes)
1st dimension
tr (minutes)
2nd dimension
X19
38.0
X20
Proposed identity
Derived from
1.97
3,5-di-tert-butyl-4-hydroxyphenyl + unknown
Derived from pentaerythritol
tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
No
38.3
1.99
unknown
Reaction/breakdown product
No
X21
40.8
1.66
unknown
Reaction/breakdown product
No
X22
45.5
2.14
unknown
Reaction/breakdown product
No
unknown
Derived from poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4-piperidinyl)imino]1,6-hexanediyl-[(2,2,6,6tetramethyl-4-piperidinyl)imino]],
No
X23
48.1
1.95
- 156 -
Predicted
Table 24. Overview of additives analysed by LC-MS
Ethanol
Isooctane#
Component
tr
(min)
APCI
neg
APCI
pos
Diparamethyldibenzylidene sorbitol
13.2
445.2
387.2
419.3
Tris(2,4-di-tert-butylphenyl)phosphite
29.8
647.5
647.5
Pentaerythritol tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
24.4
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]1,3,5-triazine-2,4-diyl]-[(2,2,6,6tetramethyl-4-piperidinyl)imino]-1,6hexanediyl-[(2,2,6,6-tetramethyl-4piperidinyl)imino]],
*
Poly(4-hydroxy-2,2,6,6-tetramethyl-1piperidine ethanol-alt-1,4-butanedioic
acid),
*
Erucamide
*
Calcium carbonate
*
APCI
pos
1175.8 1194.8 1173.6 1194.8
21.6
Glycerol monostearate
APCI
neg
338.4
Ethylenebis(oxyethylene)bis-(3-(5-tertbutyl-4-hydroxy-m-tolyl)-propionate)
17.6
TNPP
32.7
689.5
689.5
DEHP
22.0
391.3
391.3
Bis(stearoyl)ethylenediamide
28.7
593.6
16.2
400.4
+ x44
(max.
620)
400.3
+ x44
(max.
620)
Polyethylene glycol 4-tert-octyl-phenyl
ether, n~5
16.2
356.22
+x44
(max.
488)
356.2
+ x44
(max.
488)
2-(2'-Hydroxy-5'methylphenyl)benzotriazole
16.2
224.1
2-(2H-Benzotriazole-2-yl)-4,6-bis(1methyl-1-phenylethyl)phenol
21.5
446.3
Hexanedioic acid polymer with 1,3benzenedimethanamine
*
Copper phthalocyanine blue
*
Polyethylene glycol 4-tert-octyl-phenyl
ether, n=9-10
585.4
604.4
448.4
585.3
446.2
604.4
448.2
* 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
(minutes)
EtOH/isooctane
m/z (-)
m/z (+)
Proposed identity
13.2
445.2
(M-CH3COOH)-
387.2
(M+H)+
diparamethyldibenzylidene sorbitol
13.6
255.2
unknown
14.9
283.3
unknown
15.0
15.5
430.2
341.3
unknown
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
18.6
713.4
341.2
18.7/9.3
19.0
255.2
655.4
20.3
283.3
unknown
unknown
1051.7
19.4
20.6
unknown
882.6
19.1
unknown
unknown
unknown
341.3
unknown
1165.8
unknown
- 158 -
Estimated concentration
(mg/dm2)
EtOH/isooctane
7.5
Table 25 continued. Additional peaks observed for PP + additives with LC-MS
Retention time
(minutes)
EtOH/isooctane
m/z (-)
22.1
987.6
m/z (+)
Proposed identity
unknown
22.2/12.4
934.7
unknown
22.3/12.5
915.6
unknown
23.0
971.6
unknown
23.2
1119.7
23.6
1138.8
unknown
468.4
unknown
23.8
915.6
24.4/14.3
1175.8 (M-H)-
1194.8 (M+NH4)+
27.4/17.3
473.3 (M-DTBP)-
663.5 (M+H)+
unknown
28.7/18.4
29.7/19.5
579.5
457.3 (M-DTBP)
30.5
Estimated concentration
(mg/dm2)
EtOH/isooctane
-
647.5 (M+H)
607.6
pentaerythritol tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
5/125
oxidised tris(2,4-di-tert-butylphenyl)phosphite
unknown
+
tris(2,4-di-tert-butylphenyl)phosphite
unknown
DTBP = ditertbutylphenyl
- 159 -
42/112
Table 26. Additional peaks observed for PS + additives with LC-MS
Retention time
(minutes)
EtOH/isooctane
m/z (-)
16.3/7.0
17.9/8.6
m/z (+)
356.3 + x44
585.3 (M-H)-
604.4 (M+NH4)+
Proposed identity
polyethylene glycol 4-tert-octyl-phenyl ether,
n~5/polyethylene glycol 4-tert-octyl-phenyl ether,
n=9-10
ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4hydroxy-m-tolyl)-propionate)
22.0/12.5
391.3 (M+H)+
26.8
565.6
29.6/19.4
705.5 (M+H)+
oxidised TNPP
-/22.2
689.5 (M+H)+
TNPP
DEHP
Estimated concentration
(mg/dm2)
EtOH/isooctane
0.50
0.28/3.3
3.5/35
unknown
0.013/1.5
Table 27. Additional peaks observed for PET + additives with LC-MS
Retention time
(minutes)
EtOH/isooctane
m/z (-)
17.1
768.2
21.5
446.2
27.8
m/z (+)
Proposed identity
Estimated concentration
(mg/dm2)
EtOH/isooctane
unknown
448.2
2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1phenylethyl)phenol
610.2
unknown
- 160 -
0.13
Table 28. Identities of the additional peaks observed for PP + additives with LC-FT-MS
Retention time
(minutes)
EtOH/isooctane
m/z (-)
13.2
445.1894
387.1799 C22H26O6
2.0
diparamethyldibenzylidene sorbitol
13.6
255.2330
C16H32O2
0.5
hexadecanoic acid
Yes
14.9
283.2638
C18H36O2
0.6
hectadecanoic acid
Yes
1.8
1.8
1.8
unknown
No
C20H38O4
0.1
unknown
No
C31H55O9N2
C39H54O2N1P1
2.0
2.0
unknown
No
768.5358 C49H73O3N2P1
2.0
unknown
No
Elemental composition*
Mass accuracy
Proposed identity
(ppm)
C29H35O1P1
430.2433 C21H36O8N1
C20H30O3N8
15.0
15.5
m/z (+)
341.2699
15.9/6.7
599.3900
16.5
Predicted
Additive
17.6/8.3
291.1961
C18H28O3
0.1
methyl-3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate
Yes
18.3
305.2119
C19H30O3
1.3
ethyl-3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate
Yes
1.1
2.9
4.8
unknown
No
0.8
unknown
No
C35H56O7N9
713.4130 C37H58O8N6
C38H54O4N10
18.4
18.6
341.1967
C18H30O6
- 161 -
Table 28 continued. Identities of the additional peaks observed for PP + additives with LC-FT-MS
Retention time
(minutes)
EtOH/isooctane
m/z (-)
18.7/9.3
19.0
255.2332
19.1
19.4
655.4231
20.3
283.2646
22.2/12.4
Elemental composition*
Mass accuracy
Proposed identity
(ppm)
Predicted
882.5685
C45H75O8N10
C47H77O9N7
C48H73O5N11
0.1
1.4
2.9
unknown
No
313.2733
C16H32O2 (-)
C19H36O3 (+)
1.0
hexadecanoic acid
glycerol monohexadecanoate – H2O
Yes
No
C57H96O10N8
1051.7172 C55H94O9N11
C58H92O6N12
0.5
0.8
1.8
unknown
No
C39H60O8
0.1
unknown
No
C18H36O2 (-)
C21H40O3 (+)
1.0
stearic acid
glycerol monostearate – H2O
Yes
No
0.6
1.0
1.0
1.7
1.7
unknown
No
C59H88O12
2.2
pentaerythritol tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)- DTBP
No
C64H87O3P1
C55H82O5N8
C56H88O10N1
0.8
1.1
1.5
unknown
No
341.3047
C60H100O12N11
C73H102O10N2
1165.7496 C72H96O5N9
C61H96O8N15
C62H102O13N8
20.6
22.1
m/z (+)
987.6181
934.6387
- 162 -
Table 28 continued. Identities of the additional peaks observed for PP + additives with LC-FT-MS
Retention time
(minutes)
EtOH/isooctane
m/z (-)
22.3/12.5
915.6072
C60H85O5P1
C67H80O2
1.1
1.4
unknown
No
23.0
971.6290
C63H89O6P1
C59H88O11
3.5
3.7
unknown
No
23.2
1119.7186 1138.7584 C69H100O12
3.0
pentaerythritol tetrakis(3,5-di-tert-butyl4-hydroxyhydrocinnamate)– C4H8 (tertbutyl)
No
C29H58O3N1
0.7
unknown
No
C56H84O10
0.9
unknown
No
23.6
23.8
m/z (+)
468.4414
915.6002
Elemental composition*
Mass accuracy
Proposed identity
(ppm)
24.4/14.3
1175.7781 1194.8201 C73H108O12
1.5
pentaerythritol tetrakis(3,5-di-tert-butyl4-hydroxyhydrocinnamate)
27.4/17.3
473.2815
28.7/18.4
29.7/19.5
30.5
457.2898
Predicted
Additive
663.4524
C42H63O4P
1.0
oxidised tris(2,4-di-tertbutylphenyl)phosphite
Yes
579.5339
C35H69O3N2
C38H67N4
1.1
4.0
unknown
No
647.54592 C42H63O3P
1.0
tris(2,4-di-tert-butylphenyl)phosphite
607.5649
2.0
unknown
C40H71N4
Additive
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
(minutes)
EtOH/isooctane
m/z (-)
16.3/7.0
17.9/8.6
585.3412
m/z (+)
Elemental composition*
356.3 +
x44
-
Mass accuracy
Proposed identity
(ppm)
-
Predicted
polyethylene glycol 4-tert-octyl-phenyl
ether, n~5/polyethylene glycol 4-tertoctyl-phenyl ether, n=9-10
Additive
604.3824
C34H50O8
1.5
ethylenebis(oxyethylene)bis-(3-(5-tertbutyl-4-hydroxy-m-tolyl)-propionate)
Additive
22.0/12.5
391.2839
C24H38O4
1.8
DEHP
Additive
26.8
565.5660
C36H72O2N2
2.0
N,N-bis(stearoyl)ethylenediamide related
substance
No
29.6/19.4
705.4997
C45H69O4P
2.0
tris(nonylphenyl) phosphate
Yes
-/22.2
689.5049
C45H69O3P
2.0
TNPP
Additive
* elemental composition after correction for positive/negative charge and adducts (if known), see corresponding Table in the LC-MS section
(Table 26)
- 164 -
Table 30. Identities of the additional peaks observed for PET + additives with LC-FT-MS
Retention time
(minutes)
EtOH/isooctane
m/z (-)
17.1
768.1655
21.5
446.2229
27.8
m/z (+)
Elemental composition*
Mass accuracy
Proposed identity
(ppm)
C38H30O15N3
C36H29O14N6
1.7
1.7
unknown
448.2382
C30H29N3O
1.0
2-(2H-benzotriazole-2-yl)-4,6-bis(1methyl-1-phenylethyl)phenol
610.2021
-
unknown
Predicted
No
Additive
No
* elemental composition after correction for positive/negative charge and adducts (if known), see corresponding Table in the LC-MS section
(Table 27)
- 165 -
Table 31. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with +ve ESI
Additive
Retention time
(minutes)
Mass
Elemental composition
Mass error (ppm)
HDPE
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
8.7 – 10.5
338.0957
Greater than 5 matches with
mass error < 5 ppm
NA
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
18.1
246.0810
Greater than 5 matches with
mass error < 5 ppm
NA
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
46.9 – 47.8
498.2083
Greater than 5 matches with
mass error < 5 ppm
NA
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
60.1
406.2057
Greater than 5 matches with
mass error < 5 ppm
NA
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
62.3
536.1410
Greater than 5 matches with
mass error < 5 ppm
NA
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
64.4
610.1604
Greater than 5 matches with
mass error < 5 ppm
NA
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
66.0
684.1795
Greater than 5 matches with
mass error < 5 ppm
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)
Mass
Elemental composition
Mass error (ppm)
Oleamide
57.6
255.2562
C16H33NO
-0.058
Oleamide
59.1 – 59.7
281.2719
C18H35NO
(oleamide)
0.12
Oleamide
61.8
283.2875
C18H37NO
-0.053
Additive
HDPE
TiO2
No peaks detected
N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine
13.2 - 19.0
287.2719
C17H37NO2
(N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine C13)
1.8
N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine
19.7 - 25.0
315.3137
C19H41NO2
(N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine C15)
1.6
N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine
31.3
343.3450
C21H45NO2
(N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine C17)
-0.088
59.8, 60.4, 60.8
356.2927
C21H40O4
(glycerol monooleate)
0.11
Sodium (C10-C18) alkyl sulfonate
35.6
300.2301
C17H32O4
0.13
Sodium (C10-C18) alkyl sulfonate
51.6
302.2457
C17H34O4
-0.033
Sodium (C10-C18) alkyl sulfonate
55.5
328.2614
C19H36O4
1.8
Sodium (C10-C18) alkyl sulfonate
57.8
354.2770
C21H38O4
-0.028
Sodium (C10-C18) alkyl sulfonate
58.8
430.2369
C25H34O4
3.1
Glycerol monooleate
- 167 -
Table 31 continued. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with +ve ESI
Additive
Retention time
(minutes)
Mass
Elemental composition
Mass error (ppm)
59.6
330.2770
C19H38O4
-0.030
HDPE
Sodium (C10-C18) alkyl sulfonate
2,5-Bis(5'-tert.butylbenzoxazol-2yl)thiophene
No peaks detected
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
Dioctyltin bis(2-ethylhexyl thioglycolate)
16.0
238.0346
Greater than 5 matches with
mass error < 5 ppm
NA
Dioctyltin bis(2-ethylhexyl thioglycolate)
19.2
360.2148
C18H32O7
-0.010
Dioctyltin bis(2-ethylhexyl thioglycolate)
31.0
314.0855
Greater than 5 matches with
mass error < 5 ppm
NA
ESBO
62.0
364.2250
C21H32O5
0.070
ESBO
64.8
406.2203
C19H34O9
0.041
Stearic acid
Acetyltributyl citrate
Paraffin wax
No peaks detected
56.3
402.2254
No peaks detected
- 168 -
C20H34O8
(Acetyltributyl citrate)
0.078
Table 31 continued. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with +ve ESI
Additive
Retention time
(minutes)
Mass
PA
Talc
No peaks detected
Zinc stearate
No peaks detected
- 169 -
Elemental composition
Mass error (ppm)
Table 32. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with -ve ESI
Additive
Retention time
(minutes)
Mass
Elemental composition
Mass error (ppm)
42.5
252.1725
Greater than 5 matches with
mass error < 5 ppm
NA
476.1687
Greater than 5 matches with
mass error < 5 ppm
NA
HDPE
Tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Octadecyl 3,5-di-t-butyl-4hydroxyhydrocinnamate
Eucamide
TiO2
No peaks detected
55.7 – 59.2
No peaks detected
N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine
24.4
423.3196
Greater than 5 matches with mass
error < 5 ppm
NA
N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine
26.9
349.2828
C18H39NO5
-0.068
N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine
29.9
312.1759
Greater than 5 matches with mass
error < 5 ppm
NA
N,N-Bis-(2-hydroxyethyl)alkyl(C13C15)amine
32.0
451.3509
Greater than 5 matches with mass
error < 5 ppm
NA
60.0, 60.5, 61.0
402.2981
C22H42O6
(glycerol monooleate + CH2O2)
-0.098
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
Glycerol monooleate
- 170 -
Table 32 continued. Overview of peaks observed in the chromatograms when the additives were analysed by LC-TOF-MS with -ve ESI
Additive
Retention time
(minutes)
Mass
Elemental composition
Mass error (ppm)
34.1 – 39.2
320.2378
C23H30N
(unsaturated amine)
-0.078
284.2715
C18H36O2
(stearic acid)
-0.10
HDPE
Sodium (C10-C18) alkyl sulfonate
2,5-Bis(5'-tert.butylbenzoxazol-2yl)thiophene
No peaks detected
PVC
Dioctyltin bis(ethylmaleate)
No peaks detected
Dioctyltin bis(2-ethylhexyl thioglycolate)
No peaks detected
ESBO
No peaks detected
Stearic acid
66.0
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
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
14.3 – 21.2
243.2562
17.9
C15H33NO
-0.061
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
secondary amine C13
Yes
14.4 – 16.4
287.2824
1000
C17H37NO2
1.8
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C13
Additive
14.6 – 30.1
331.3086
Not
measurable*
C19H41NO3
-0.13
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C13 (-2H) + CH2CH2OH
No
19.7 – 22.5
285.2668
12.6
C17H35NO2
0.071
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C13 (-2H)
No
20.0 – 21.7
303.2926
Not
measurable*
C21H39N
-0.0016
unsaturated amine
No
21.0
269.2719
Not
measurable*
C17H35NO
0.12
C15 unsaturated mono alcohol derivative
No
21.5 – 29.9
271.2875
88.4
C17H37NO
-0.055
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
secondary amine C15
Yes
21.9 – 29.5
315.3137
947
C19H41NO2
1.6
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C15
Additive
22.5 – 29.9
359.3399
Not
measurable*
C21H45NO3
1.4
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C15 (-2H) + CH2CH2OH
No
30.8
313.2981
Not
measurable*
C19H39NO2
0.064
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C15 - 2H
No
- 172 -
Proposed identity
Predicted
Table 33 continued. Positive ESI analysis of the ethanol extracts of the HDPE (final solvent acetonitrile) – substances that were only detected
in the HDPE + additives extracts
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
31.2 – 34.7
343.3450
1260
C21H45NO2
-0.088
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C17 (present in standard)
No
35.7
369.3243
Not
measurable*
C22H43NO3
0.014
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
unsaturated C16 derivative
No
42.8
227.2249
674
C14H29NO
-0.065
unknown (present in oleamide standard)
No
50.0, 53.0
253.2406
589
C16H31N
0.13
unsaturated amine (present in oleamide
standard)
No
54.2, 56.5
328.2614
Not
measurable*
C19H36O4
0.12
C17 aliphatic chain di-acid (present in sodium
(C10-C18) alkyl sulfonate standard)
No
55.6 – 57.2
279.2562
589
C18H33NO
-0.053
unknown (present in oleamide standard)
No
57.6
255.2562
Not
measurable*
C16H33NO
-0.058
C14 unsaturated mono alcohol derivative
(present in oleamidestandard)
No
59.0 – 59.6
281.2719
863
C18H35NO
0.12
oleamide
Additive
59.9, 60.5,
60.9
356.2927
2630
C21H40O4
0.11
glycerol monooleate
Additive
Proposed identity
* Not measurable as no peak was observed in the TIC and therefore the peak area could not be compared with the internal standard
- 173 -
Predicted
Table 34. Positive ESI analysis of the isooctane extracts of the HDPE (final solvent acetonitrile) – substances that were only detected in the
HDPE + additives extracts
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
27.6 – 30.2
287.2824
103
C17H37NO2
1.8
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C13
Additive
27.8 – 31.3
331.3086
Not
measurable*
C19H41NO3
1.5
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C13 + CH2CH2OH
No
34.0 – 38.3
315.3137
71.6
C19H41NO2
1.6
N,N-bis-(2-hydroxyethyl)alkyl(C13-C15)amine
C15
Additive
34.5 – 39.6
359.3399
Not
measurable*
C21H45NO3
1.4
C21H45NO3 (C15H30N(CH2CH2OH)2 +
CH2CH2OH)
No
56.9
338.2457
Not
measurable*
C20H34O4
1.6
unknown
No
57.7, 58.0
278.1518
Not
measurable*
C16H22O4
1.9
dibutyl phthalate (isomers)
No
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
Proposed identity
* Not measurable as no peak was observed in the TIC and therefore the peak area could not be compared with the internal standard
- 174 -
Predicted
Table 35. Negative ESI analysis of the ethanol extracts of the HDPE (final solvent acetonitrile) – substances that were only detected in the
HDPE + additives extracts
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
23.9 – 27.3
278.1882
Not
measurable*
C17H26O3
0.018
unknown
No
27.6 – 30.0
292.2068
Not
measurable*
C21H26N
0.94
unsaturated amine
No
30.5 – 34.4
306.2225
Not
measurable*
C22H28N
1.0
unsaturated amine
No
34.9 – 40.0
320.2378
Not
measurable*
C23H30N
-0.078
unsaturated amine
No
60.0, 60.6,
61.1
402.2981
Not
measurable*
C22H42O6
-0.098
glycerol monooleate + CH2O2
No
Proposed identity
* Not measurable as no peak was observed in the TIC and therefore the peak area could not be compared with the internal standard
- 175 -
Predicted
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
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
3.3 – 4.5
190.0841
Not
measurable*
C8H14O5
0.23
unknown
No
5.6
172.0736
Not
measurable*
C8H12O4
-0.12
unknown (present in dioctyltin bis(ethylmaleate)
standard)
No
8.4
264.0676
Not
measurable*
C8H12O4
-0.12
unknown
No
12.4
276.1222
Not
measurable*
C12H20O7
4.6
unknown
No
12.9 – 14.4
218.1154
Not
measurable*
C10H18O5
2.4
unknown (present in dioctyltin bis(ethylmaleate)
standard)
No
15.3
432.2547
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
15.8
191.1310
Not
measurable*
C12H17NO
-0.074
unknown
No
16.7 – 17.2
238.0346
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown (present in dioctyltin bis(2-ethylhexyl
thioglycolate) standard)
No
18.8
304.1529
Not
measurable*
C14H24O7
2.2
unknown
No
19.9
318.1318
Not
measurable*
C14H22O8
1.0
unknown
No
- 176 -
Proposed identity
Predicted
Table 36 continued. Positive ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in
the PVC + additives extracts
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
21.4
304.1529
Not
measurable*
C14H24O7
2.2
unknown
No
23.1, 24.3,
28.9
346.1634
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
25.8, 26.4
386.2671
Not
measurable*
C21H38O6
0.67
unknown
No
27.9
390.2984
Not
measurable*
C21H42O6
0.66
unknown
No
30.3
336.2903
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
31.4
354.2415
Not
measurable*
C20H34O5
2.4
unknown
No
32.2, 33.2
416.2087
Not
measurable*
C20H32O9
2.6
unknown
No
35.7
358.2805
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
38.0
374.1961
Not
measurable*
C20H29O8
0.11
unknown
No
- 177 -
Proposed identity
Predicted
Table 36 continued. Positive ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in
the PVC + additives extracts
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
40.0
360.1248
Not
measurable*
C18H32O7
-0.010
Proposed identity
unknown (present in dioctyltin bis(2-ethylhexyl
thioglycolate) standard)
* Not measurable as no peak was observed in the TIC and therefore the peak area could not be compared with the internal standard
- 178 -
Predicted
No
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
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
3.0
190.0841
Not
measurable*
C8H14O5
-0.12
unknown
No
7.6
366.1923
Not
measurable*
C18H22O8
-6.6
unknown
No
10.6 – 26.6
402.2261
Not
measurable*
C20H34O8
1.8
unknown
No
19.3
318.1318
Not
measurable*
C14H22O8
1.0
unknown
No
20.5 – 23.0
246.1467
Not
measurable*
C12H22O5
-0.097
unknown
No
25.6
346.1641
Not
measurable*
C16H26O8
3.8
unknown
No
29.9 – 30.7
418.2216
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
32.2 – 38.5
416.2087
Not
measurable*
C20H32O9
4.1
unknown
No
39.5
374.1961
Not
measurable*
C20H29O8
-2.1
unknown
No
- 179 -
Proposed identity
Predicted
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
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
41.0
360.2148
Not
measurable*
C18H32O7
-0.010
Proposed identity
unknown (present in dioctyltin bis(2-ethylhexyl
thioglycolate) standard)
* Not measurable as no peak was observed in the TIC and therefore the peak area could not be compared with the internal standard
- 180 -
Predicted
No
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
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
1.9
264.0661
Not
measurable*
C8H22O4
1.3
unknown
No
4.5
214.1205
Not
measurable*
C11H18O4
-0.043
unknown
No
8.4
228.1362
Not
measurable*
C12H20O4
0.17
unknown
No
12.9
242.1518
Not
measurable*
C13H22O4
-0.038
unknown
No
16.0 – 16.4
450.2829
Not
measurable*
C22H42O9
0.036
unknown
No
19.5 – 20.8
456.2762
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
24.0
422.2880
Not
measurable*
C21H42O8
-1.2
unknown
No
25.7 – 26.5
432.2571
Not
measurable*
C31H32N2
1.2
unknown
No
28.0
436.3045
Not
measurable*
C22H44O8
2.0
unknown
No
30.2
442.2931
Not
measurable*
C24H42O7
0.10
unknown
No
- 181 -
Proposed identity
Predicted
Table 38 continued. Negative ESI analysis of the ethanol extracts of the PVC (final solvent acetonitrile) – substances that were only detected in
the PVC + additives extracts
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
36.0
404.2774
Not
measurable*
C21H40O7
-0.010
unknown
No
40.1 – 41.8
418.2957
Not
measurable*
C25H40NO4
-0.081
unknown
No
43.5
782.5234
Not
measurable*
C54H69O4
-3.4
unknown
No
54.4
376.2852
Not
measurable*
C21H44O2
4.8
unknown
No
56.7
586.3532
Not
measurable*
C34H50O8
4.4
unknown
No
59.9
744.5093
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
62.4
726.4979
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
64.0
730.5355
Not
measurable*
C54H68N
0.44
unsaturated amine
No
Proposed identity
* Not measurable as no peak was observed in the TIC and therefore the peak area could not be compared with the internal standard
- 182 -
Predicted
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
Retention
time
(minutes)
Mass
Estimated
concentration
(µg/dm2)
Elemental composition
Mass
accuracy
(ppm)
9.3
228.1362
Not
measurable*
C12H20O4
0.17
unknown
No
13.7
242.1518
Not
measurable*
C13H22O4
-0.038
unknown
No
44.9
432.2571
Not
measurable*
C31H32N2
1.2
unknown
No
56.8
586.3532
Not
measurable*
C34H50O8
4.4
unknown
No
61.7
541.9472
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown – Contains Cl atoms
No
62.5
726.4979
Not
measurable*
Greater than 5 matches
with mass error < 5 ppm
NA
unknown
No
Proposed identity
Predicted
* 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
PP
5000000
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
PP + additives
5000000
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
HDPE + additives
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
Time-->
- 186 -
25.00
30.00
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
PS + additives
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-->
- 187 -
Figure 4. Thermodesorption GC-MS chromatograms of PET and PET + additives
Abundance
TIC: FSA007.D
PET
500000
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
5e+07
4.8e+07
PVC
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
Time-->
- 189 -
25.00
30.00
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
Time-->
- 190 -
25.00
30.00
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
94112133
0
50
100
281
169188207 239258
311 342361
150
200
250
300
399 429
350
400
450
350
400
450
m/z-->
Abundance
#799: 2-Propanone, 1-hydroxy43
9000
8000
7000
6000
5000
4000
3000
2000
74
1000 15
0
50
100
150
200
m/z-->
- 191 -
250
300
Figure 8. Best library match of the peak eluting at retention time 12.9 minutes in the
thermodesorption GC-MS chromatogram of the HDPE + additives sample
Abundance
Average of 12.871 to 12.910 min.: rxn_230107_010.D (-)
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
350
400
m/z-->
Abundance
#918: Propylene Glycol
45
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
0
27
76
50
100
150
200
m/z-->
- 192 -
250
300
Figure 9. Best library match of the peak eluting at retention time 7.0 minutes in the
thermodesorption GC-MS chromatogram of the PVC + additives sample
Abundance
Average of 6.876 to 7.027 min.: rxn_230107_015.D (-)
31
9000
8000
7000
6000
5000
4000
3000
2000
1000
51 73 96
0
0
50
100
133 165183 207227250
150
200
250
286 311 343362385 415433
300
350
400
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
m/z-->
- 193 -
250
Figure 10. Best library match of the peak eluting at retention time 11.2 minutes in the
thermodesorption GC-MS chromatogram of the PVC + additives sample
Abundance
Average of 11.203 to 11.262 min.: rxn_230107_015.D (-)
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
0
74
20 40 60 80 100120140160180200220240260280300320340360380400420
m/z-->
- 194 -
Figure 11. Best library match of the peak eluting at retention time 19.1 minutes in the
thermodesorption GC-MS chromatogram of the PVC + additives sample
Abundance
Average of 19.027 to 19.085 min.: rxn_230107_015.D (-)
57
9000
8000
7000
6000
5000
4000
3000
83
2000
1000
31
112
0
50
100
141 166 197 232252 276296315 343362384403 432
150
200
250
300
350
400
450
350
400
450
m/z-->
Abundance
#13220: 1-Hexanol, 2-ethyl57
9000
8000
7000
6000
5000
4000
3000
2000
83
29
1000
112
0
50
100
150
200
m/z-->
- 195 -
250
300
Figure 12. GC-MS chromatograms of ethanol extracts of PP and PP + additives full
scale and zoomed in to show low intensity peaks
Abundance
4e+07
TIC: FSA_013.D
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
35.00
40.00
45.00
35.00
40.00
45.00
35.00
40.00
45.00
Time-->
Abundance
4e+07
TIC: FSA_015.D
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
Time-->
Abundance
1600000
TIC: FSA_013.D
PP
1400000
1200000
1000000
800000
600000
400000
200000
0
10.00
15.00
20.00
25.00
30.00
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
Time-->
- 196 -
30.00
Figure 13. GC-MS chromatograms of isooctane extracts of PP and PP + additives full
scale and zoomed in to show low intensity peaks
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
30.00
35.00
40.00
Time-->
Abundance
PP + additives
TIC: FSA_091.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
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
35.00
40.00
45.00
35.00
40.00
45.00
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
Time-->
Abundance
TIC: FSA_198.D
3500000
3000000
PP
2500000
2000000
1500000
1000000
500000
0
5.00
10.00
15.00
20.00
25.00
30.00
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
Time-->
- 198 -
30.00
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
TIC: RXN_LSCREEN_160207_022.D
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
TIC: RXN_LSCREEN_160207_020.D
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
TIC: RXN_LSCREEN_160207_022.D
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
TIC: RXN_LSCREEN_060207_014.D
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-->
HDPE + additives
Abundance
TIC: RXN_LSCREEN_060207_017.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-->
Abundance
HDPE
8000000
TIC: RXN_LSCREEN_060207_014.D
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
TIC: RXN_LSCREEN_060207_017.D
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
TIC: RXN_LSCREEN_160207_027.D
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
TIC: RXN_LSCREEN_160207_029.D
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
TIC: RXN_LSCREEN_160207_027.D
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
TIC: RXN_LSCREEN_160207_029.D
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
HDPE
TIC: RXN_LSCREEN_060207_020.D
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
HDPE
TIC: RXN_LSCREEN_060207_020.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-->
Abundance
HDPE + additives
TIC: RXN_LSCREEN_060207_023.D
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-->
- 202 -
Figure 19. GC-MS chromatograms of ethanol extracts of PS and PS + additives full
scale and zoomed in to show low intensity peaks
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
35.00
40.00
45.00
35.00
40.00
45.00
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
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
Time-->
Abundance
400000
PS + additives
TIC: FSA_041.D
350000
300000
250000
200000
150000
100000
50000
0
10.00
15.00
20.00
25.00
Time-->
- 203 -
30.00
Figure 20. GC-MS chromatograms of isooctane extracts of PS and PS + additives full
scale and zoomed in to show low intensity peaks
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
30.00
35.00
40.00
30.00
35.00
40.00
30.00
35.00
40.00
Time-->
Abundance
PS + additives
TIC: FSA_111.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
Tim
e-->
Abundance
TIC: FSA_109.D
3000000
PS
2500000
2000000
1500000
1000000
500000
0
5.00
10.00
15.00
20.00
25.00
Time-->
Abundance
TIC: FSA_111.D
3000000
PS + additives
2500000
2000000
1500000
1000000
500000
0
5.00
10.00
15.00
20.00
Time-->
- 204 -
25.00
Figure 21. GC-MS chromatograms of the concentrated ethanol extracts PS and PS +
additives full scale and zoomed in to show low intensity peaks
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
35.00
40.00
45.00
35.00
40.00
45.00
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
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
Time-->
Abundance
TIC: FSA_203.D
PS + additives
2500000
2000000
1500000
1000000
500000
0
5.00
10.00
15.00
20.00
25.00
Time-->
- 205 -
30.00
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
30.00
35.00
40.00
30.00
35.00
40.00
30.00
35.00
40.00
Time-->
Abundance
PS + additives
TIC: FSA_218.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
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
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
Time-->
- 206 -
25.00
Figure 23. GC-MS chromatograms of ethanol extracts of PET and PET + additives
Abundance
200000
TIC: FSA_028.D
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
35.00
40.00
45.00
Time-->
Abundance
200000
180000
TIC: FSA_030.D
PET + additives
160000
140000
120000
100000
80000
60000
40000
20000
0
10.00
15.00
20.00
25.00
Time-->
- 207 -
30.00
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
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
Time-->
- 208 -
25.00
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
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
Time-->
Abundance
TIC: FSA_196.D
140000
PET
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
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
Time-->
- 209 -
32.00
34.00
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
3000000
TIC: FSA_213.D
PET
2500000
2000000
1500000
1000000
500000
0
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
30.00
35.00
40.00
Time-->
Abundance
3000000
PET + additives
TIC: FSA_214.D
2500000
2000000
1500000
1000000
500000
0
5.00
10.00
15.00
20.00
25.00
Time-->
Abundance
500000
TIC: FSA_213.D
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
35.00
40.00
Time-->
Abundance
500000
PET + additives
TIC: FSA_214.D
450000
400000
350000
300000
250000
200000
150000
100000
50000
5.00
10.00
15.00
20.00
Time-->
- 210 -
25.00
30.00
Figure 27. GC-MS chromatograms of ethanol extracts of PVC and PVC + additives full
scale and zoomed in to show low intensity peaks
Abundance
TIC: RXN_LSCREEN_160207_032.D
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
TIC: RXN_LSCREEN_160207_035.D
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
TIC: RXN_LSCREEN_060207_027.D
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
TIC: RXN_LSCREEN_060207_030.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
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
scale and zoomed in to show low intensity peaks
Abundance
TIC: RXN_LSCREEN_160207_070.D
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
TIC: RXN_LSCREEN_160207_073.D
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
TIC: RXN_LSCREEN_160207_070.D
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
TIC: RXN_LSCREEN_160207_073.D
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
TIC: RXN_LSCREEN_060207_063.D
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
TIC: RXN_LSCREEN_060207_066.D
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 +
additives full scale and zoomed in to show low intensity peaks
Abundance
TIC: RXN_LSCREEN_160207_076.D
5e+07
PA
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
TIC: RXN_LSCREEN_160207_079.D
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
TIC: RXN_LSCREEN_160207_076.D
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
TIC: RXN_LSCREEN_160207_079.D
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 +
additives full scale and zoomed in to show low intensity peaks
Abundance
TIC: RXN_LSCREEN_060207_069.D
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
TIC: RXN_LSCREEN_060207_072.D
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
TIC: RXN_LSCREEN_060207_069.D
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
TIC: RXN_LSCREEN_060207_072.D
800000
750000
700000
PA + additives
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
4.00
6.00
8.00 10.00
12.00
14.00
16.00
18.00
20.00
22.00
24.00
26.00
28.00
30.00
Time-->
- 216 -
Figure 33. GCxGC-TOF-MS chromatograms of ethanol extracts of (A) PP and (B) PP
+ additives
A
B
- 217 -
Figure 34. GCxGC-TOF-MS chromatograms of isooctane extracts of (A) PP and (B)
PP + additives
A
B
- 218 -
Figure 35. GCxGC-TOF-MS chromatograms of concentrated ethanol extracts of (A)
PP and (B) PP + additives
A
B
- 219 -
Figure 36. GCxGC-TOF-MS chomatograms of ethanol extracts of (A) HDPE and (B)
HDPE + additives
A
B
- 220 -
Figure 37. GCxGC-TOF-MS chromatograms of isooctane extracts of (A) HDPE and
(B) HDPE + additives
A
B
- 221 -
Figure 38. GCxGC-TOF-MS chromatograms of concentrated ethanol extracts of (A)
HDPE and (B) HDPE + additives
A
B
- 222 -
Figure 39. GCxGC-TOF-MS chromatograms of concentrated isooctane extracts of (A)
HDPE and (B) HDPE + additives
A
B
- 223 -
Figure 40. GCxGC-TOF-MS chromatograms of ethanol extracts of (A) PS and (B) PS
+ additives
A
B
- 224 -
Figure 41. GCxGC-TOF-MS chromatograms of isooctane extracts of (A) PS and (B)
PS + additives
A
B
- 225 -
Figure 42. GCxGC-TOF-MS chromatograms of concentrated ethanol extracts of (A)
PS and (B) PS + additives
A
B
- 226 -
Figure 43. GCxGC-TOF-MS chromatograms of concentrated isooctane extracts of (A)
PS and (B) PS + additives
A
B
- 227 -
Figure 44. GCxGC-TOF-MS chromatograms of concentrated ethanol extracts of (A)
PET and (B) PET + additives
A
B
- 228 -
Figure 45. GCxGC-TOF-MS chromatograms of concentrated isooctane extracts of (A)
PET and (B) PET + additives
A
B
- 229 -
Figure 46. GCxGC-TOF-MS chromatograms of concentrated ethanol extracts of (A)
PA and (B) PA + additives
A
B
- 230 -
Figure 47. GCxGC-TOF-MS chromatograms of concentrated isooctane extracts of (A)
PA and (B) PA + additives
A
B
- 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=
150.00-1250.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
EtOH_APCI_NEG-03
100
PP APCI-
90
Relative Abundance
80
70
60
50
40
30
20
10
0
NL: 3.08E7
Base Peak m/z=
150.00-1250.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_neg-06
24.37
1175.77
100
PP + additives APCI-
90
Relative Abundance
80
70
60
50
40
30
13.19
445.19
20
27.42
29.67
473.28 457.29
22.29
915.60
17.61
291.20
10
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=
150.00-1200.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
EtOH_APCI_POS_03
100
PP APCI+
90
Relative Abundance
80
70
60
50
40
30
20
10
27.44
29.81
680.48 647.46
0
24.40
1194.82
100
29.74
647.46
PP + additives APCI+
90
Relative Abundance
80
NL: 1.10E8
Base Peak m/z=
150.00-1200.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_pos_05
70
60
50
40
30
20
13.18
387.18
10
18.66
882.57
0
0
5
10
15
27.44
663.45
22.26
934.64
20
Time (min)
- 233 -
25
30.41
607.56
30
35
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
100
NL: 5.09E6
Base Peak m/z=
150.00-1250.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_neg_04
PP APCI-
90
Relative Abundance
80
70
60
50
40
30
20
14.44
17.18
1175.77 473.28
10
0
NL: 5.09E6
Base Peak m/z=
150.00-1250.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_neg_05
14.32
1175.77
100
PP + additives APCI-
90
Relative Abundance
80
70
60
50
40
30
14.45
1175.78
20
12.47
915.60
8.27
291.20
10
19.42
457.29
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
14.45
1194.82
PP APCI+
90
80
Relative Abundance
NL: 5.42E7
Base Peak m/z=
150.00-1200.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
ISOOCT_APCI_POS_03
19.53
647.46
100
17.34
663.45
70
60
50
40
30
20
13.90
934.64
10
20.55
647.46
0
NL: 1.84E8
Base Peak m/z=
150.00-1200.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_pos_05
19.44
647.46
100
PP + additives APCI+
90
Relative Abundance
80
70
14.35
1194.82
60
33.21
599.55
50
40
17.28
663.45
30
20.14
647.46
20
9.34
5.89
430.24 882.57
10
0
0
5
10.74
996.61
10
21.34
647.46
15
20
Time (min)
- 234 -
32.15
599.55
25
30
35
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
529.46
100
NL: 2.57E6
Base Peak m/z=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_neg-24
PS APCI-
90
Relative Abundance
80
70
60
50
18.59
341.20
40
30
23.15 23.82
341.20 341.20
15.02
283.26
20
27.53
341.20
6.83
9.25
11.54
341.20 341.20 341.20
3.27
341.20
10
0
29.85
341.20
NL: 2.44E6
Base Peak m/z=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_neg-26
17.92
585.34
100
PS + additives APCI-
90
Relative Abundance
80
70
60
50
40
30
26.70
20.91 22.06 529.46
341.20 341.20
27.40
358.42
20
15.03
283.26
1.69
3.47
6.67
9.37
341.20 341.20 341.20 341.20
10
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
100
NL: 5.84E6
Base Peak m/z=
150.00-1000.00 F: FTMS + c
APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_pos_24_0702150
05635
PS APCI+
90
Relative Abundance
80
70
60
50
40
0.60
420.26
30
20
2.27
420.26
10
3.91
420.26
0
44.71
420.26
32.24
33.28
403.23 403.23
21.98
395.31
21.97
391.28
100
NL: 5.84E6
Base Peak m/z=
150.00-1000.00 F: FTMS + c
APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_pos_26
PS + additives APCI+
90
Relative Abundance
80
70
60
17.93
604.38
50
40
4.85
420.26
30
20
10
5.72
420.26
7.78
420.26
16.33
444.33
10.26
420.26
26.78
565.57
26.57
936.75
29.61
705.50
31.54
403.23
35.43
403.23
0
0
5
10
15
20
25
Time (min)
30
- 235 -
35
40
44.43
420.26
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=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_neg_24
PS APCI-
100
90
Relative Abundance
80
70
60
50
40
30
20
10
0
NL: 4.64E6
Base Peak m/z=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_neg_25
8.59
585.34
100
PS + additives APCI-
90
Relative Abundance
80
70
60
50
40
30
20
9.21
341.20
10
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
100
NL: 2.21E7
Base Peak m/z=
150.00-1000.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_pos_24
PS APCI+
90
Relative Abundance
80
70
60
50
40
30
20
9.21
420.26
10
0
NL: 2.21E7
Base Peak m/z=
150.00-1000.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_pos_25
12.40
391.28
100
90
19.54 22.19
647.46 403.23
15.57
403.23
PS + additives APCI+
Relative Abundance
80
70
60
50
40
8.56
604.38
30
19.33
705.50
7.01
444.33
20
12.73
391.28
10
18.50
403.23
22.31
689.51
23.13
703.52
0
5
10
15
Time (min)
20
- 236 -
25
30
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=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_neg-16
100
PET APCI-
90
Relative Abundance
80
70
16.06
576.13
60
50
40
30
20
11.01
251.13
10
15.65
622.17
25.22
23.98
358.42 923.55
17.07
768.17
0
29.17
30.74
358.42 923.57
NL: 1.13E6
Base Peak m/z=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_neg-18
21.50
446.22
100
PET + additives APCI-
90
Relative Abundance
80
70
16.07
576.13
60
50
40
30
20
10.91
251.13
10
15.63
622.17
17.07
768.16
20.30
537.64
24.42
358.42
30.86 32.97
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
395.41
100
PET APCI+
90
Relative Abundance
80
70
60
50
40
30
21.98
395.31
20
16.05
577.13
4.04
395.31
10
0
28.67
27.80 607.57
607.57
21.49
448.24
100
PET + additives APCI+
90
33.00
395.41
80
Relative Abundance
NL: 2.33E5
Base Peak m/z=
150.00-1000.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_pos_16
NL: 2.22E5
Base Peak m/z=
150.00-1000.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
etoh_apci_pos_18
70
60
50
40
30
21.97
395.31
20
16.06
577.13
2.66
5.26
395.31 264.17
10
0
0
5
10
20.95
860.29
15
20
Time (min)
- 237 -
27.78
610.18
26.69
537.63
30.06
684.20
25
30
35
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
537.64 Base Peak m/z=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
ISOOCT_APCI_NEG_15
100
90
PET APCI-
Relative Abundance
80
70
60
0.66
655.42
50
40
2.45
655.42
30
6.79
9.26
576.13 358.42
14.20
358.42
27.36 29.62
358.42 358.42
21.54
358.42
17.73
358.42
20
10
0
0.94
655.42
100
7.36
358.42
3.31
655.42
90
10.95
12.26
358.42 358.42
23.62
358.42
17.20
19.17
358.42 537.64
NL: 1.07E3
Base Peak m/z=
150.00-1000.00 F: FTMS
- c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_neg_18
30.96
33.11
28.52
358.42 358.42 358.42
Relative Abundance
80
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
NL: 2.71E5
Base Peak m/z=
150.00-1000.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_pos_16
19.52
647.46
100
90
PET APCI+
Relative Abundance
80
70
17.28
663.45
60
50
40
30
0.13
420.26
20
2.28
420.26
10
9.23
403.23
20.51
403.23
16.20
13.45
403.23 403.23
0
22.13
403.23
24.15 26.08
403.23 403.23
31.16
403.23
NL: 3.60E5
Base Peak m/z=
150.00-1000.00 F: FTMS
+ c APCI corona Full ms [
150.00-1500.00] MS
isooct_apci_pos_18
19.52
647.46
100
90
Relative Abundance
80
PET + additives APCI+
70
60
17.29
663.45
50
40
20.68
403.23
30
20
2.60
403.23
10
3.72
420.26
9.23
403.23
12.43
395.31
16.40
403.23
21.97
403.23
23.61
403.23
25.86
403.23
28.76
403.23
0
0
5
10
15
Time (min)
20
- 238 -
25
30
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,
final solvent acetonitrile) in positive mode electrospray TOF-MS
- 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,
final solvent acetonitrile) in negative mode electrospray TOF-MS
- 246 -
Figure 63. Total ion chromatogram for PA and PA + additives (isooctane extraction,
final solvent acetonitrile) in positive mode electrospray TOF-MS
- 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,
final solvent acetonitrile) in negative mode electrospray TOF-MS
- 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
butanedioic acid
PP additive 6 = Erucamide
- 252 -
ethanol-alt-1,4-
Figure 69.
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. 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
butanedioic acid
PP additive 6 = Erucamide
- 253 -
ethanol-alt-1,4-
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 -
Figure 71.
Stacked 1H 1D NMR spectroscopy plot of the additives used in the
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 -
Figure 72.
Stacked 1H 1D NMR spectroscopy plot of the additives used in 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
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 -
Figure 74.
Stacked 1H 1D NMR spectroscopy plot of the additives used in the
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 -
Figure 76.
Stacked 1H 1D NMR spectroscopy plot of the additives used in the
preparation of the PET test materials compared to the PET extracts and PET +
additives extracts
2-(2H-Benzotriazole-2-yl)-4,6-bis(1-methyl-1phenylethyl)phenol
PET blank
PET + additives
- 260 -
Figure 77.
Stacked 1H 1D NMR spectroscopy plot of the additives 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
- 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 -
Figure 79.
Stacked 1H 1D NMR spectroscopy plot of the additives used in the
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 -
Figure 82.
1
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 -
Figure 84.
1
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 -
Figure 85.
13
C–1H HSQC NMR spectrum of the region 1H = 5.4 – 3.0 and 13C = 80 – 45
ppm of the PP + additives extract
- 269 -
Figure 86.
13
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-tertbutyl-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 -
Figure 87.
13
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-tertbutylphenyl)phosphite were analysed by GC-MS
2,4-DI-T-BUTYL PHENOL – impurity in or breakdown product of tris(2,4-di-tertbutylphenyl)phosphite
Abundance
Average of 11.536 to 11.741 min.: rxn_060307_041.D (-)
191
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
57
1500
1000
74 91
500
0
40
40
60
163
115
133
208
267
230249
291
325
355
387
415
80 100120140160180200220240260280300320340360380400420
m/z-->
- 273 -
UNKNOWN – impurity in or breakdown product of tris(2,4-di-tert-butylphenyl)phosphite
Abundance
Average of 22.507 to 22.574 min.: rxn_060307_041.D (-)
17000
57
16000
281
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
197
147
2000
91
1000
237
175
117
219
255
0
40
60
329
311
357
385
416 441
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(2,4-di-tert-butylphenyl)phosphite
Abundance
Average of 27.073 to 27.097 min.: rxn_060307_041.D (-)
385
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
57
8000
7000
6000
5000
147
441
4000
3000
2000
97
1000
78
0
40
60
119
175
210
313
237
255
355
273293
331
404
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 274 -
TRIS(2,4-DI-TERT-BUTYLPHENYL)PHOSPHITE ISOMER
Abundance
Average of 27.187 to 27.206 min.: rxn_060307_041.D (-)
60000
441
55000
50000
45000
40000
35000
30000
25000
20000
57
15000
10000
308
147
5000
91
191
235
253
173
210
117
0
385
329
284
413
359
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
TRIS(2,4-DI-TERT-BUTYLPHENYL)PHOSPHITE
Abundance
Average of 27.301 to 27.401 min.: rxn_060307_041.D (-)
441
5000000
4500000
4000000
3500000
3000000
57
2500000
2000000
147
1500000
1000000
308
500000
191
91
119
173
0
40
60
237
219
273
255
291
385
329
347367
411
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
Average of 28.542 to 28.618 min.: rxn_120307_003.D (-)
316
210000
200000
190000
180000
170000
160000
150000
57
140000
130000
120000
110000
100000
90000
80000
70000
60000
191
50000
40000
147
30000
91
20000
253
291
117
367
10000
173
222
0
40
60
345
271
443
403423
385
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-
hydroxyhydrocinnamate)
Abundance
Average of 16.206 to 16.344 min.: rxn_060307_042.D (-)
277
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
5000
0
147
219
57
91
128
109
185
249
167
295
327
355
387
415 442
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-
hydroxyhydrocinnamate)
Abundance
Average of 16.881 to 17.015 min.: rxn_060307_042.D (-)
291
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
147
219
3500
3000
2500
57
2000
1500
189
1000
91
128
500
109
0
40
60
171
249
267
341
320
387
415
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 277 -
Mass spectra of peaks detected when the solvent standards of poly[[6-[(1,1,3,3tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4piperidinyl)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-[(2,2,6,6TETRAMETHYL-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][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4piperidinyl)imino]]
Abundance
Average of 22.446 to 22.522 min.: rxn_060307_043.D (-)
98
124
9500
9000
8500
8000
58
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
237
2000
1500
1000
0
256
181
155
500
79
40
40
60
209
296
315
336
394 416
356
376
441
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-4piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]
Abundance
Average of 29.950 to 30.059 min.: rxn_060307_043.D (-)
124
55000
50000
45000
40000
58
35000
321
30000
25000
20000
209
15000
98
10000
348
5000
0
235
167
40
79
147
191
253
388
275
293
418 444
370
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of poly(4-hydroxy2,2,6,6-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
Average of 20.139 to 20.192 min.: rxn_060307_045.D (-)
15000
59
14000
13000
12000
11000
10000
9000
8000
7000
6000
41
5000
4000
81
3000
126
2000
100
154
1000
238 264
178198 220
282
326
0
356
401
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 21.219 to 21.290 min.: rxn_060307_045.D (-)
32000
55
30000
28000
26000
24000
22000
83
20000
122
18000
16000
14000
12000
319
10000
276
150
8000
178
6000
206
248
4000
2000
103
0
40
224
295
341
401
359 383
429
60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 280 -
ETHYL-13-DOCOSENOATE – impurity in or breakdown product of erucamide
Abundance
Average of 21.789 to 21.808 min.: rxn_060307_045.D (-)
55
8500
8000
7500
7000
6500
6000
5500
5000
83
320
4500
4000
3500
3000
101
2500
2000
123
1500
1000
236
500
278
207
155
366
179
254
302
341
388
415
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
EICOSENAMIDE – impurity in or breakdown product of erucamide
Abundance
Average of 21.827 to 21.846 min.: rxn_060307_045.D (-)
59
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
41
14000
12000
10000
83
8000
126
6000
309
4000
154
2000
101
0
40
60
266
207
226 248
182
284
341
366
401
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 281 -
EICOSENAMIDE – impurity in or breakdown product of erucamide
Abundance
Average of 21.884 to 21.899 min.: rxn_060307_045.D (-)
8500
59
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
41
1000
86
207
114
154
178
134
500
281
235
309
341
262
387
430
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 22.160 to 22.341 min.: rxn_060307_045.D (-)
55
6000
5500
5000
4500
4000
83
3500
122
193
3000
2500
2000
319
1500
276
150
220
1000
248
500
103
168
295
0
40
60
339358
385
417
441
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 282 -
ERUCAMIDE
Abundance
Average of 23.382 to 23.663 min.: rxn_060307_045.D (-)
59
1800000
1600000
1400000
1200000
1000000
800000
600000
41
83
400000
337
126
200000
154
101
184
212
240 263
294
0
319
355
387
415
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
ERGOSTA-4,6,22-TRIENE – impurity in or breakdown product of erucamide
Abundance
Average of 24.471 to 24.500 min.: rxn_060307_045.D (-)
380
5000
4500
4000
3500
3000
2500
81
207
255
2000
55
1500
105
145
1000
281
123
500
175
228
355
313 337
0
40
60
402
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 283 -
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 24.562 to 24.581 min.: rxn_060307_045.D (-)
96
5000
55
4500
4000
3500
3000
2500
2000
1500
124
265
418
1000
399
152
500
191
220
292
245
77
327
345
173
371
445
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 24.590 to 24.614 min.: rxn_060307_045.D (-)
6500
55
6000
5500
5000
82
4500
4000
3500
3000
2500
418
110
2000
1500
207
138
341
1000
268
500
180
161
306
396
235
286
369
447
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 284 -
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 24.871 to 24.933 min.: rxn_120307_007.D (-)
382
2800
2600
2400
2200
2000
1800
1600
1400
147
1200
1000
43
430
800
81
105
600
261
213
400
129
295
192
173
200
235
63
0
40
60
403
326
344
80 100120140160180200220240260280300320340360380400420440
m/z-->
TETRACOSENAMIDE – impurity in or breakdown product of erucamide
Abundance
Average of 24.819 to 24.852 min.: rxn_060307_045.D (-)
59
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
41
83
365
10000
114
5000
0
135154
207
184
322
281
240 263
304
341
385
415
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 285 -
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 24.895 to 24.923 min.: rxn_060307_045.D (-)
382
12000
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
147
5500
5000
4500
4000
105
3500
3000
2500
274
255
2000
213
1500
1000
58
500
129
79
173
191
238
0
40
60
320
356
401
298
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 25.251 to 25.266 min.: rxn_060307_045.D (-)
396
5000
4500
4000
3500
3000
207
2500
2000
91
43
1500
147
255
1000
69
281
119
341
177
500
429
228
0
40
60
312
373
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 286 -
UNKNOWN – impurity in or breakdown product of erucamide
Abundance
Average of 25.470 to 25.503 min.: rxn_060307_045.D (-)
396
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
147
9000
8000
43
7000
6000
81
105
5000
4000
207
255
275
3000
129
2000
173
1000
228
296
61
0
40
60
327
355
373
415
443
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
Average of 16.815 to 16.891 min.: rxn_060307_046.D (-)
88
120000
110000
100000
90000
80000
70000
60000
50000
40000
43
30000
284
157
20000
10000
0
241
70
115
139
199
219
175
306
263
341
401
383
429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 287 -
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance
Average of 17.980 to 18.056 min.: rxn_060307_046.D (-)
117
4500
4000
3500
3000
2500
2000
75
1500
1000
45
500
191
96
137
165
265
283
223
241
325
356
0
40
60
385
415
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
OCTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monostearate
Abundance
Average of 18.684 to 18.798 min.: rxn_060307_046.D (-)
88
220000
200000
180000
160000
140000
120000
100000
80000
43
312
60000
40000
20000
0
157
269
69
213
115
139
185
241
295
341
369
387
415
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 288 -
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance
Average of 19.388 to 19.450 min.: rxn_060307_046.D (-)
130
4000
3500
3000
2500
2000
1500
207
1000
343
57
101
500
281
177
325
75
157
229 251
0
40
60
369
299
403
431
80 100120140160180200220240260280300320340360380400420440
m/z-->
EICOSANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monostearate
Abundance
Average of 20.386 to 20.448 min.: rxn_060307_046.D (-)
88
6500
6000
5500
5000
4500
4000
3500
3000
43
340
2500
117
2000
157
1500
297
207
69
1000
500
255
135
40
60
359
185
227
0
279
315
401
383
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 289 -
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance
Average of 21.043 to 21.147 min.: rxn_060307_046.D (-)
130
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
371
30000
43
20000
239
101
71
315
190
10000
149 171
0
40
259
208
343
281
401
429
447
60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance
Average of 21.414 to 21.937 min.: rxn_060307_046.D (-)
117
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
313
15000
43
207
10000
75
98
147
5000
171
189
0
40
60
281
239
259
371
341
389 415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 290 -
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance
Average of 22.641 to 22.774 min.: rxn_060307_046.D (-)
130
120000
110000
100000
90000
80000
70000
60000
50000
40000
399
30000
43
101
267
20000
71
343
203
10000
149
173
221 245
0
285
371
315
429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance
Average of 22.931 to 23.111 min.: rxn_060307_046.D (-)
117
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
341
20000
18000
16000
14000
12000
10000
207
8000
6000
4000
73
98
147
281
414
2000
54
0
40
60
171
189
227
259
315
371
389
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 291 -
UNKNOWN – impurity in or breakdown product of glycerol monostearate
Abundance
Average of 23.430 to 23.554 min.: rxn_060307_046.D (-)
415
26000
24000
22000
20000
18000
191
16000
14000
12000
10000
133
8000
221
6000
4000
163
73
281
43
2000
95
114
0
239 261
311 333
355
387
445
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-ditert-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-tertbutylphenyl)[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
91
163
115
133
209
0
40
60
251
281
316
342
415
441
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average
1600
of
18.156
to
18.180
min.:
rxn_060307_021.D
(-)
57
1500
1400
1300
1200
85
1100
1000
900
800
700
600
111
500
210
400
355
300
200
415
141
40
182
100
265
282
163
325
246
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
- 293 -
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 18.218 to 18.242 min.: rxn_060307_021.D (-)
57
2000
1800
1600
85
1400
1200
1000
800
111
600
210
400
200
265
141
179
161
40
341
283
387
369
430
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 18.275 to 18.337 min.: rxn_060307_021.D (-)
57
900
800
85
700
600
500
111
400
300
192
282
211
200
135
100
429
163
251
357
309329
40
401
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
- 294 -
SUBSTITUTED BIPHENYL – impurity in or breakdown product of tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
Abundance
Average of 18.427 to 18.532 min.: rxn_060307_021.D (-)
246
2400
154
2200
218
2000
1800
1600
1400
1200
1000
55
800
600
83
400
127
199
177
200
267
297
0
40
60
415
327
102
356
387
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
SUBSTITUTED BIPHENYL – impurity in or breakdown product of tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
Abundance
Average of 18.755 to 18.912 min.: rxn_060307_021.D (-)
218
55000
50000
45000
246
154
40000
35000
30000
25000
20000
15000
10000
5000
51
0
115
77
96
134
199
181
283
265
401
312
330 356 383
429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 295 -
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average
of
19.022
to
19.088
min.:
rxn_060307_021.D
(-)
57
1600
1500
1400
1300
1200
85
1100
1000
900
800
700
224
600
111
500
400
300
174
200
282
207
249
100
325
148
356
130
415
432
378
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
SUBSTITUTED BIPHENYL – impurity in or breakdown product of tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
Abundance
Average of 24.971 to 24.990 min.: rxn_060307_021.D (-)
338
4500
152
282
4000
219
3500
3000
2500
2000
1500
247
1000
310
97
65
500
126
201
183
416
47
358
385
441
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 296 -
SUBSTITUTED BIPHENYL – impurity in or breakdown product of tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]-4,4’-diylphosphonite
Abundance
Average of 25.290 to 25.323 min.: rxn_060307_021.D (-)
282
32000
30000
28000
26000
24000
338
22000
152
20000
18000
16000
219
14000
12000
10000
8000
309
247
6000
201
4000
2000
65
47
83
0
40
60
102
183
126
357
389
429
411
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 25.274 to 25.376 min.: RXN_800_310307_005.D (-)
595
200000
180000
160000
140000
120000
100000
290
80000
57
60000
349
40000
147 191
20000
539
91
389
252
441
483
637
0
50
100
150
200
250
300
350
400
m/z-->
- 297 -
450
500
550
600
650
699
730 772
700
750
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 25.902 to 25.979 min.: RXN_800_310307_005.D (-)
347
38000
36000
291
34000
32000
30000
28000
26000
24000
57
22000
20000
552
18000
16000
14000
12000
10000
8000
427
6000
91
4000
147
191
495
2000
235
396
0
50
100
150
200
250
300
350
400
595 638
461
450
500
550
600
697
650
700
754
750
m/z-->
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 26.378 to 26.420 min.: RXN_800_310307_005.D (-)
385
60000
55000
50000
441
45000
40000
35000
30000
57
25000
20000
590
15000
91
147
10000
280
5000
191 237
329
475 519
551
0
50
100
150
200
250
300
350
400
m/z-->
- 298 -
450
500
550
624
600
679
711 757
650
700
750
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 27.006 to 27.031 min.: RXN_800_310307_005.D (-)
385
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
57
12000
590
10000
441
8000
147
6000
280
207
4000
91
2000
329
249
475
506 550
0
50
100
150
200
250
300
350
400
450
500
550
638
600
650
698
752
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
Average of 27.244 to 27.303 min.: RXN_800_310307_005.D (-)
441
5000000
4500000
4000000
3500000
3000000
2500000
2000000
57
1500000
646
147
1000000
308
500000
191
91
237
385
273
0
50
100
150
200
250
300
345
350
477
400
m/z-->
- 299 -
450
533
500
550
589
600
698 738
771
650
700
750
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 29.247 to 29.315 min.: RXN_800_310307_005.D (-)
389
160000
150000
140000
130000
120000
333
110000
100000
90000
80000
594
70000
60000
57
50000
40000
282
30000
20000
183
91
10000
495
461
219
0
50
100
537
427
147
150
200
250
300
350
400
450
639
500
550
600
650
697 738
772
700
750
800
m/z-->
UNKNOWN – impurity in or breakdown product of tetrakis(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4’-diylphosphonite
Abundance
Average of 30.427 to 30.529 min.: RXN_800_310307_005.D (-)
389
1200000
1100000
1000000
900000
800000
700000
600000
500000
333
400000
594
300000
57
200000
183
100000
91
427
282
147
235
50
100
150
200
250
537
495
462
0
300
350
400
m/z-->
- 300 -
450
500
637
550
600
650
698 744 786
700
750
Mass spectra of peaks detected when the solvent standards of octadecyl 3,5-di-tbutyl-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
Average of 16.123 to 16.200 min.: RXN_800_310307_006.D (-)
277
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
147
10000
8000
219
57
6000
4000
91
2000
185
356
327
0
50
100
150
200
250
300
350
401
400
475
450
500
550
550
711
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-4Abundance
Average of 16.834 to 16.891 min.: rxn_060307_022.D (-)
291
260000
240000
220000
200000
180000
160000
140000
120000
100000
147
219
80000
60000
57
40000
20000
0
91
40
40
74
60
129
109
189
249
171
273
308
341360
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 301 -
OCTADECYL 3,5-DI-T-BUTYL-4-HYDROXYHYDROCINNAMATE
Abundance
Average of 28.721 to 28.874 min.: RXN_800_310307_006.D (-)
530
4500000
4000000
3500000
3000000
2500000
2000000
1500000
219
57
1000000
500000
147
97
278
185
317
0
50
100
150
200
250
300
374 416
350
400
474
450
564
500
550
623 664
697736
771
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
Average of 16.563 to 16.615 min.: rxn_060307_023.D (-)
59
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
600
41
400
83
112
200
137
154 177
225
208
40
60
355
251
0
283
401
311
328
429
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
2000
128
111
184 207
227
156
40
60
281
251
0
327
355
385
415
80 100120140160180200220240260280300320340360380400420
m/z-->
HEXADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of
oleamide
Abundance
Average of 16.844 to 16.853 min.: rxn_060307_023.D (-)
88
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
57
2500
2000
41
284
1500
157
1000
241
115
199
500
141
177
218
0
40
60
267
308
341
357
403
80 100120140160180200220240260280300320340360380400420
m/z-->
- 303 -
PENTADECANAMIDE – impurity in or breakdown product of oleamide
Abundance
Average of 17.395 to 17.495 min.: rxn_060307_023.D (-)
59
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
41
86
500
114
198
147 170
241
221
0
355
281 304325
385
415
448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of oleamide
Abundance
Average of 17.719 to 17.785 min.: rxn_060307_023.D (-)
55
10500
10000
122
9500
9000
8500
8000
7500
7000
6500
6000
83
5500
5000
4500
4000
150
3500
220
3000
2500
263
178
2000
1500
1000
105
500
198
0
40
60
241
281 304
341
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 304 -
OXADECANITRILE – impurity in or breakdown product of oleamide
Abundance
Average of 17.923 to 17.976 min.: rxn_060307_023.D (-)
72
750
700
650
600
550
110
500
450
400
43
350
300
150
250
208
180
200
236
150
263
100
342
91
429
50
283
133
314
385
409
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
HEXADECENAMIDE – impurity in or breakdown product of oleamide
Abundance
Average of 18.413 to 18.470 min.: rxn_060307_023.D (-)
59
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
41
80000
60000
40000
98
126
253
20000
79
0
40
60
154
210
192
235
172
281
310
341
383
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 305 -
HEXADECANAMIDE – impurity in or breakdown product of oleamide
Abundance
Average of 18.589 to 18.637 min.: rxn_060307_023.D (-)
59
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
200000
41
86
100000
128
212
255
170
109
0
40
60
147
194
237
277
312
342
385
403
429448
80 100120140160180200220240260280300320340360380400420440
m/z-->
HEPTADECANAMIDE – impurity in or breakdown product of oleamide
Abundance
Average of 19.264 to 19.307 min.: rxn_060307_023.D (-)
40000
59
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
41
6000
4000
86
128
226
2000
111
0
40
60
170
153
269
198
252
326
308
356
385
415
432
80 100120140160180200220240260280300320340360380400420
m/z-->
- 306 -
HEPTADECENAMIDE – impurity in or breakdown product of oleamide
Abundance
Average of 19.312 to 19.416 min.: rxn_060307_023.D (-)
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
147
100
1000
224
168 193
500
249
295
0
40
60
327
357
385
416
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
OLEAMIDE
Abundance
Average of 20.225 to 20.334 min.: rxn_060307_023.D (-)
59
3500000
3000000
2500000
2000000
1500000
41
1000000
126
98
500000
79
0
281
154
238
184
220
263
202
313 338
356
385
415
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 307 -
OCTADECANOIC ACID, BUTYL ESTER – impurity in or breakdown product of
oleamide
Abundance
Average of 20.363 to 20.377 min.: rxn_060307_004.D (-)
285
4500
4000
3500
3000
2500
267
56
2000
340
1500
129
1000
241
500
185
168
108
75
212
146
323
0
40
60
415
356 378397
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
Average of 20.410 to 20.429 min.: rxn_060307_023.D (-)
59
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
200000
41
86
100000
240
128
283
156
0
40
60
184
212
261
326
355
383404 430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 308 -
DI-(2-ETHYLHEXYL) PHTHALATE – impurity in or breakdown product of oleamide
Abundance
Average of 21.504 to 21.542 min.: rxn_060307_023.D (-)
149
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
167
4000
3500
3000
2500
57
2000
279
1500
113
1000
83
500
207
187
131
0
40
60
237
255
325
297
355
417
399
381
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
ICOSENAMIDE – impurity in or breakdown product of oleamide
Abundance
Average of 21.851 to 21.980 min.: rxn_060307_023.D (-)
59
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
41
5000
4000
81
3000
126
2000
309
100
1000
154
180
212 235
0
40
60
266 290
343
369
399
429
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-(2hydroxyethyl)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
Average of 10.186 to 10.281 min.: rxn_060307_006.D (-)
57
3500
3000
2500
2000
85
1500
1000
500
113
40
198
141
40
169
0
60
281
225
253
327
355
401
430
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
Average of 11.522 to 11.622 min.: rxn_060307_006.D (-)
191
50000
45000
40000
35000
30000
25000
20000
15000
10000
57
5000
74 91
0
40
40
60
115
133
163
208
225 250
281
309327
401
355
429
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 14.666 to 14.708 min.: rxn_060307_025.D (-)
86
2400
2200
2000
1800
1600
1400
1200
1000
800
600
400
56
200
105
133
152
193
211
238
0
40
60
327
267
284
415
355
387
80 100120140160180200220240260280300320340360380400420
m/z-->
- 311 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 14.723 to 14.765 min.: rxn_060307_025.D (-)
86
2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
135
600
400
56
107
200
165
0
40
60
343
194
268
211 234
251
323
385
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 14.913 to 14.941 min.: rxn_060307_006.D (-)
86
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
56
1000
224
500
0
107 131149
168
40
40
60
207
254
282
327
355
401
417
80 100120140160180200220240260280300320340360380400420
m/z-->
- 312 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 15.198 to 15.289 min.: rxn_060307_006.D (-)
86
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
56
1000
135
500
112
0
40
60
154
177
224
207
254
282
341
370
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 15.954 to 16.016 min.: rxn_060307_006.D (-)
100
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
163
209
282
55
79
0
40
60
80
116134
192
234253
327
357
401
417
100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->
- 313 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 16.311 to 16.406 min.: rxn_060307_006.D (-)
86
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
254
7000
6000
5000
4000
3000
56
2000
224
1000
112 135
0
40
60
163182 207
281
325
342
369
401
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average
100
of
16.848
to
16.896
min.:
rxn_060307_006.D
(-)
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
341
207
500
269
75
51
415
134
165 189
0
40
60
224
250
296
369
447
80 100
120
140
160
180200
220
240
260
280300
320
340
360
380400
420
440
m/z-->
- 314 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 17.314 to 17.338 min.: rxn_060307_006.D (-)
174
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
130
1000
500
43
73
328
100
149
192
221
253
281
0
40
60
303
356
387
416
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 17.381 to 17.410 min.: rxn_060307_006.D (-)
174
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
130
1000
500
75
43
0
40
60
107
328
156
193
210
228 249268
295
356
402
385
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 315 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 17.519 to 17.538 min.: rxn_060307_006.D (-)
86
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
56
2000
282
1000
117 140
176196
157
0
40
60
341
252
223
373 399
431
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 17.552 to 17.590 min.: rxn_060307_006.D (-)
174
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000
130
328
207
1000
0
40
40
59
60
85 107
147
224
253
281
311
356
401
383
431
80 100120140160180200220240260280300320340360380400420
m/z-->
- 316 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 17.885 to 17.909 min.: rxn_060307_006.D (-)
174
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
130
4000
328
2000
43
75
0
40
60
102
156
192
224 251
356
282301
401
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 17.933 to 17.975 min.: rxn_060307_025.D (-)
100
5000
4500
4000
3500
3000
2500
2000
174
1500
1000
144
500
41
70
125
193
221
251
0
40
60
283
328
357
385
416
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 317 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 18.213 to 18.266 min.: rxn_060307_006.D (-)
174
110000
100000
90000
80000
70000
60000
50000
40000
30000
20000
130
328
10000
43
75
0
40
60
100
200 224242 268
147
298
345
385403
430
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 18.280 to 18.313 min.: rxn_060307_006.D (-)
86
10500
10000
9500
9000
8500
8000
282
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
56
1500
1000
252
500
126145
107
0
40
60
172
194
212 234
356
300 323
379
403
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 318 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 18.375 to 18.413 min.: rxn_060307_006.D (-)
174
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
130
328
5000
43
75
0
103
150
194
224 251
281
298
358 383403 430
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 18.770 to 18.808 min.: rxn_060307_006.D (-)
100
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
248
2500
2000
1500
1000
207
55 73
500
137
118
0
40
60
281
161
178
224
298 323342
371
399
416
433
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 319 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 19.060 to 19.103 min.: rxn_060307_006.D (-)
174
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000
328
20000
10000
114
43
61
0
40
60
86
224
145
200
248 270
298
356
383
415
433
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 19.145 to 19.193 min.: rxn_060307_006.D (-)
174
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000
328
20000
130
10000
43
75
0
40
60
100
154
200
224
242
270
298
356
403 429
385
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 320 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 19.683 to 19.702 min.: rxn_060307_006.D (-)
174
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
130
1000
356
281
500
57
77
102
211
154
0
40
60
253
235
299
403
384
325
432
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 19.783 to 19.821 min.: rxn_060307_006.D (-)
248
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
402
2000
1500
133
1000
500
107
43
73
163
40
60
342
204
224
282
182
0
304324
360 385
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 321 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 19.906 to 19.954 min.: rxn_060307_025.D (-)
114
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
224
4500
4000
3500
3000
86
2500
2000
1500
1000
58
500
0
140
40
40
60
248
168
283
196
309 330
358
386
416
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 19.987 to 20.058 min.: rxn_060307_006.D (-)
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
43
207
73
0
40
60
100
151
230
252
281
328
310
396415
441
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 322 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 20.058 to 20.096 min.: rxn_060307_025.D (-)
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
43
73
100
0
40
60
207
150
281
252
235
396
327
309
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 20.777 to 20.905 min.: rxn_060307_006.D (-)
174
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
356
10000
5000
130
43
207
73
96
0
154
248
228
281
300 326
385404 429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 323 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 20.924 to 20.967 min.: rxn_060307_025.D (-)
210
7000
6500
6000
5500
5000
4500
4000
3500
154
3000
238
112
2500
2000
1500
188
1000
281
73
500
329
55
92
0
256
135
307
355
396
378
415
443
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 21.033 to 21.090 min.: rxn_060307_025.D (-)
210
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
238
4000
3500
168
3000
2500
2000
1500
43
98
1000
140
267
69
500
294
118
188
0
40
60
322
350
385
417
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 324 -
UNKNOWN – impurity in or breakdown product of N-bis-(2-hydroxyethyl)alkyl(C13C15)amine
Abundance
Average of 21.252 to 21.333 min.: rxn_060307_025.D (-)
210
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
253
2000
281
84
1500
43
154 179
1000
61
500
112
132
40
60
327
308
235
0
355
387
429
404
447
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
Average of 14.818 to 14.903 min.: rxn_060307_026.D (-)
88
5000
4500
4000
3500
3000
2500
2000
1500
43
1000
157
70
211
256
500
115
134
282
177
233
0
40
60
309328
357
383
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 325 -
HEXADECENOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance
Average of 16.634 to 16.725 min.: rxn_060307_026.D (-)
55
4000
3500
3000
88
2500
2000
194
1500
237
152
111
1000
500
282
129
175
342
219
265
0
40
60
311
371
402
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
HEXADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance
Average of 16.839 to 16.939 min.: rxn_060307_026.D (-)
88
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
43
2500
284
2000
157
70
1500
241
1000
115
500
199
137
0
40
60
175
219
265
343
306
385
325
367
403
429
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 326 -
HEPTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of
glycerol monooleate
Abundance
Average of 17.523 to 17.543 min.: rxn_060307_026.D (-)
88
2800
2600
2400
2200
2000
1800
1600
117
1400
57
1200
1000
157
800
298
600
211
255
400
185
200
327
229
356
136
415
387
0
40
60
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
HEPTADECENOIC ACID, ETHYL ESTER – impurity in or breakdown product of
glycerol monooleate
Abundance
Average of 17.566 to 17.614 min.: rxn_060307_026.D (-)
55
1300
1200
1100
1000
900
101
800
83
700
600
250
500
211
400
300
166
325
133
200
296
343
100
185
229
269
402
383
431
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 327 -
LINOLEIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance
Average of 18.403 to 18.437 min.: rxn_060307_026.D (-)
67
3000
2500
95
41
2000
1500
1000
123
150
500
262
207
178
308
237
282
356
329
0
403
385
429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
OCTADECENOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance
Average of 18.465 to 18.489 min.: rxn_060307_026.D (-)
260000
55
240000
220000
200000
180000
88
160000
140000
264
120000
100000
222
80000
111
180
60000
155
137
40000
310
20000
199
246
0
40
60
282
341
371
401
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 328 -
OCTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of glycerol
monooleate
Abundance
Average of 18.689 to 18.736 min.: rxn_060307_026.D (-)
88
5500
5000
4500
4000
3500
3000
2500
2000
1500
269
312
157
43
1000
213
61
500
115
139
179
399
241
293
0
40
60
343
371
431
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of glycerol monooleate
Abundance
Average of 19.150 to 19.202 min.: rxn_060307_026.D (-)
55
1400
1300
1200
1100
1000
207
98
900
237
800
700
135
600
73
500
401
400
300
269
165
355
200
117
325
185
295
100
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
Average of 20.791 to 20.848 min.: rxn_060307_026.D (-)
55
55000
50000
45000
265
40000
98
35000
30000
25000
20000
15000
137
10000
79
221
174
117
5000
193
247
155
0
340
283
401
359 383
302322
429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of glycerol monooleate
Abundance
Average of 20.905 to 20.924 min.: rxn_060307_026.D (-)
131
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
101
4000
3000
75
2000
203
237
1000
40
173
0
40
60
355
281
384
429
259
299
328
403
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 330 -
UNKNOWN – impurity in or breakdown product of glycerol monooleate
Abundance
Average of 21.047 to 21.076 min.: rxn_060307_026.D (-)
130
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
96
2500
2000
371
239
43
1500
71
1000
315
190
281
500
149
172
208
259
344
404
432
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of glycerol monooleate
Abundance
Average of 22.431 to 22.602 min.: rxn_060307_026.D (-)
131
110000
100000
90000
80000
70000
60000
50000
40000
30000
101
20000
10000
0
55
75
203
151 173
265
221 246
283
412
316 341
369389
430
448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 331 -
UNKNOWN – impurity in or breakdown product of glycerol monooleate
Abundance
Average of 22.978 to 23.473 min.: rxn_060307_026.D (-)
117
55000
50000
45000
40000
35000
30000
25000
55
20000
15000
98
203
264
149
75
10000
412
339
175
5000
227246
0
287
315
369388
432
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
CHOLESTA-3,5-DIENE – impurity in or breakdown product of glycerol monooleate
Abundance
Average of 24.139 to 24.243 min.: rxn_060307_026.D (-)
368
5500
5000
4500
4000
3500
3000
2500
145
81
43
2000
117
247
1500
400
213
1000
285
500
163
62
190
304
0
40
60
323
445
345
99
419
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
Average of 10.162 to 10.305 min.: rxn_060307_008.D (-)
4500
57
4000
3500
3000
2500
85
2000
1500
1000
500
113
133
198
155
0
40
60
177
221
253
283
342
369
401
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
PENTADECANE – impurity in or breakdown product of sodium (C10-C18) alkyl
sulfonate
Abundance
Average of 11.456 to 11.513 min.: rxn_060307_008.D (-)
16000
57
15000
14000
13000
12000
11000
10000
9000
85
8000
7000
6000
5000
4000
3000
2000
212
112
1000
40
141
169 191
0
40
60
251
282
325
342
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 333 -
HEXADECANE – impurity in or breakdown product of sodium (C10-C18) alkyl
sulfonate
Abundance
Average of 12.597 to 12.749 min.: rxn_060307_008.D (-)
14000
57
13000
12000
11000
10000
9000
8000
85
7000
6000
5000
4000
3000
2000
113
1000
141
169
226
208
251
0
282
327
356
387 415
448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HEPTADECANE – impurity in or breakdown product of sodium (C10-C18) alkyl
sulfonate
Abundance
Average of 13.776 to 13.886 min.: rxn_060307_008.D (-)
57
12500
12000
11500
11000
10500
10000
9500
9000
8500
8000
7500
7000
85
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
113
1000
240
141
500
183
209
0
40
60
327
267
163
295
355
387
416
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 334 -
Mass spectra of peaks detected when the solvent standards of 2,5-bis(5'-tertbutylbenzoxazol-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
73
105
133
281
172
200000
387
151
0
40
359
341
239
41
60
263
299318
405
448
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-(5tert-butyl-4-hydroxy-m-tolyl)-propionate)
Abundance
Average of 15.379 to 15.436 min.: rxn_060307_049.D (-)
161
85000
80000
75000
235
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
5000
91
128
74
41
178
207
252
108
0
40
60
281
327
357
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 336 -
UNKNOWN – impurity in or breakdown product of ethylenebis(oxyethylene)bis-(3-(5tert-butyl-4-hydroxy-m-tolyl)-propionate)
Abundance
Average of 15.702 to 15.731 min.: rxn_060307_049.D (-)
175
5500
5000
4500
4000
278
3500
3000
2500
2000
1500
1000
145
500
128
91
192
217
57
74
327
249
109
0
40
60
356
415
389
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-mtolyl)-propionate)
Abundance
Average of 16.078 to 16.144 min.: rxn_060307_049.D (-)
161
1100000
1000000
900000
800000
249
700000
600000
500000
400000
300000
200000
91
100000
128
57
109
0
40
60
190
221
267
295
313
341
359 383
401
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 337 -
UNKNOWN – impurity in or breakdown product of ethylenebis(oxyethylene)bis-(3-(5tert-butyl-4-hydroxy-m-tolyl)-propionate)
Abundance
Average of 16.820 to 16.901 min.: rxn_060307_049.D (-)
291
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
147
2500
2000
219
57
88
1500
1000
177
129
500
109
199
241 267
0
325
343 369
401
429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of ethylenebis(oxyethylene)bis-(3-(5tert-butyl-4-hydroxy-m-tolyl)-propionate)
Abundance
Average of 22.883 to 23.130 min.: rxn_060307_049.D (-)
161
190
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
368
4500
4000
3500
45
3000
2500
2000
1500
247
87
1000
105 128
500
65
217
0
40
60
328
285
309
346
389
417 443
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
Average of 12.678 to 12.735 min.: rxn_060307_050.D (-)
107
8000
7500
7000
6500
135
6000
5500
5000
4500
4000
3500
3000
2500
220
2000
1500
191
57
1000
77
500
163
40
251
0
40
60
282
313
341
369389
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 12.844 to 12.906 min.: rxn_060307_050.D (-)
107
3000
2500
135
2000
1500
71
1000
220
500
355
191
43
89
281
163
251
0
40
60
327
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 339 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of
121
12.982
to
12.996
min.:
rxn_060307_050.D
(-)
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
163
1000
220
43
91
500
69
147
341
191
253
282
325
367387
416
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 13.063 to 13.096 min.: rxn_060307_050.D (-)
107
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
220
1000
500
91
150
177
43
71
267
342
131
195
0
40
60
249
325
385
416
80 100120140160180200220240260280300320340360380400420
m/z-->
- 340 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 13.324 to 13.424 min.:
135
210000
rxn_060307_050.D (-)
200000
190000
180000
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
107
40000
30000
20000
41
177
77
10000
59
0
40
60
157
220
270
251
195
296
327
355
401
383
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphate
Abundance
Average of 13.714 to 13.762 min.: rxn_060307_050.D (-)
121
450000
400000
350000
300000
250000
163
200000
150000
100000
50000
41
0
220
91
65
145
193
253
281
299
327
357 383
401
429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 341 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 13.824 to 13.857 min.: rxn_060307_050.D (-)
135
4000000
3500000
3000000
2500000
2000000
1500000
1000000
107
500000
41
220
77
161
59
0
40
60
189
249
283
313
341
383
401
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 13.933 to 13.947 min.: rxn_060307_050.D (-)
149
2000000
1800000
1600000
107
1400000
1200000
1000000
191
800000
600000
400000
220
55
77
200000
131
0
40
60
173
265
283
325
343 369389
416
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 342 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 13.966 to 13.976 min.: rxn_060307_050.D (-)
135
1600000
1400000
1200000
1000000
800000
107
600000
400000
200000
41
191
77
161
59
0
220
249
279
313
341
371
415
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 14.033 to 14.052 min.: rxn_060307_050.D (-)
135
2200000
2000000
1800000
1600000
1400000
1200000
1000000
107
800000
600000
400000
200000
191
41
59
0
40
220
77
60
163
253
281 305 329 355
386
417
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 343 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 14.166 to 14.185 min.: rxn_060307_050.D (-)
107
600000
163
550000
500000
450000
400000
350000
135
300000
250000
200000
150000
100000
41
77
220
50000
181 203
60
0
40
60
251
282
342
325
368
415
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 14.237 to 14.271 min.: rxn_060307_050.D (-)
149
900000
800000
700000
107
600000
500000
400000
177
300000
200000
100000
55
77
131
0
220
195
253
281
311
328
356 383
401
429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 344 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 14.356 to 14.380 min.: rxn_060307_050.D (-)
135
4000000
3500000
3000000
2500000
2000000
1500000
1000000
107
500000
41
77
161
58
0
40
60
191
220
251
281
325
356
374
401
430
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 14.418 to 14.456 min.: rxn_060307_050.D (-)
149
900000
800000
700000
600000
107
500000
400000
300000
200000
100000
191
55
77
220
131
0
171
251
283
327
356 383
401
429448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 345 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 14.689 to 14.723 min.: rxn_060307_050.D (-)
135
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
107
10000
163
234
5000
41
191
77
58
0
40
60
210
269
252
295
328
367387
417
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 14.827 to 14.875 min.: rxn_060307_050.D (-)
135
190000
180000
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
107
40000
30000
20000
41
10000
77
59
0
40
60
163
234
191
209
265
283
325
357
387
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 346 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 16.040 to 16.121 min.: rxn_060307_050.D (-)
161
36000
34000
32000
30000
28000
26000
24000
249
22000
20000
18000
16000
14000
12000
10000
8000
6000
135
4000
91
57
2000
190
115
221
282 307 329 355
0
40
60
387
415
432
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average
of
16.839
to
16.858
min.:
rxn_060307_050.D
291
(-)
26000
25000
24000
23000
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
147
9000
219
8000
7000
57
6000
5000
4000
88
3000
2000
129
105
1000
0
40
40
60
189
171
239 263
308
343
326
371
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 347 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 16.905 to 16.924 min.: rxn_060307_050.D (-)
255
15000
14000
13000
12000
11000
121
10000
9000
8000
7000
93
6000
5000
65
4000
3000
340
2000
1000
163
181
145
41
279
311
208227
357
0
40
60
387
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.186 to 17.219 min.: rxn_060307_050.D (-)
121
283
32000
30000
28000
26000
24000
22000
20000
18000
16000
93
14000
65
12000
10000
241
8000
6000
340
4000
149
167
43
2000
191
209
0
40
60
264
313
401
358 384
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 348 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.357 to 17.367 min.: rxn_060307_050.D (-)
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
141
0
40
60
181
199
227
274
295
312
357
387
429
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.395 to 17.409 min.: rxn_060307_050.D (-)
269
220000
200000
180000
311
160000
140000
121
120000
100000
93
80000
65
60000
40000
340
20000
43
0
149
177
195
213
237
293
373 399
429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 349 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.433 to 17.447 min.: rxn_060307_050.D (-)
121
150000
140000
269
130000
120000
110000
100000
90000
93
80000
70000
65
60000
311
50000
40000
241
30000
340
20000
43
149
10000
177
195213
0
40
60
293
358
385
402
429
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.509 to 17.533 min.: rxn_060307_050.D (-)
255
200000
121
190000
180000
170000
160000
150000
140000
130000
120000
110000
93
100000
90000
65
80000
70000
60000
311
50000
340
40000
30000
20000
163
41
181
10000
141
227
199
0
40
60
283
371
390
417
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 350 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.638 to 17.671 min.: rxn_060307_050.D (-)
269
121
140000
130000
120000
110000
100000
90000
297
80000
70000
93
60000
65
50000
40000
30000
20000
43
10000
153
177
241
195
0
40
60
340
322
358
223
385
415
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.709 to 17.728 min.: rxn_060307_050.D (-)
283
110000
100000
90000
80000
121
70000
60000
50000
40000
93
30000
65
20000
10000
0
255
41
149
167 191
227
209
325
354
387
429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 351 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.823 to 17.842 min.: rxn_060307_050.D (-)
255
500000
450000
400000
350000
121
300000
250000
200000
150000
93
65
100000
311
50000
163
181
141
199
43
0
40
60
340
283
227
385
403
431
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 17.894 to 17.918 min.: rxn_060307_050.D (-)
269
140000
130000
120000
121
110000
100000
90000
80000
70000
93
60000
50000
65
40000
30000
20000
340
43
177
10000
153
195
227
0
40
60
295
251
323
385
367
415
433
80 100120140160180200220240260280300320340360380400420
m/z-->
- 352 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 18.118 to 18.161 min.: rxn_060307_050.D (-)
255
30000
28000
26000
24000
22000
20000
18000
16000
121
14000
12000
10000
93
8000
65
6000
4000
2000
283
163
181
207227
145
43
0
354
309328
403 429
385
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 18.194 to 18.242 min.: rxn_060307_050.D (-)
255
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
121
10000
9000
8000
7000
6000
93
5000
65
4000
3000
2000
325
43
163
207
181
227
141
1000
0
40
60
281
298
354
387
416
433
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 353 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 18.284 to 18.299 min.: rxn_060307_050.D (-)
255
18000
17000
16000
15000
14000
13000
121
12000
11000
10000
9000
8000
7000
297
6000
93
5000
65
4000
3000
2000
1000
213233
141
40
325
163
181
41
0
60
354
385
279
416
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 18.389 to 18.408 min.: rxn_060307_050.D (-)
121
255
7000
6500
6000
297
5500
5000
4500
4000
3500
93
3000
65
2500
2000
1500
354
1000
500
153
43
181
205 227
0
279
324
388
416
446
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 354 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 18.641 to 18.655 min.: rxn_060307_050.D (-)
255
25000
24000
23000
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
121
9000
8000
7000
6000
5000
4000
93
65
3000
163
2000
1000
41
141
0
40
60
181201221
289
309
327
354
402
383
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 25.851 to 25.884 min.: rxn_060307_050.D (-)
90000
429
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
71
20000
15000
181
10000
295
43
5000
107
89
0
40
60
135
153
207
251
269
232
314
341
359
388 411
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 355 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 25.931 to 25.960 min.: rxn_060307_050.D (-)
429
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
71
25000
20000
15000
172
10000
43
295
107
5000
153
135
195
89
0
40
60
237
219
265
331
357
401
383
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.036 to 26.065 min.: rxn_060307_050.D (-)
429
120000
110000
100000
90000
80000
71
70000
60000
50000
165
43
40000
295
30000
20000
107127
10000
0
89
147
207
186
237
265
317 341
369
401
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 356 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of
26.107 to 26.136 min.:
rxn_060307_050.D (-)
429
105000
100000
95000
90000
85000
80000
75000
70000
65000
60000
71
55000
50000
45000
40000
165
35000
30000
43
295
25000
20000
107
127
15000
10000
209
5000
89
145
186
239
0
40
60
265
317
343 365385
411
448
80 100120140
160180200
220240260
280300
320340360
380400420
440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.202 to 26.221 min.: rxn_060307_050.D (-)
429
1000000
900000
800000
700000
600000
500000
400000
71
300000
200000
43
181
100000
107127
89
0
40
60
295
158
209
237
265
317 343
401
361 383
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 357 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.269 to 26.293 min.: rxn_060307_050.D (-)
429
900000
800000
700000
600000
500000
400000
71
300000
200000
295
43
172
153
107127
100000
195
237
219
89
0
265
317 343
401
361 383
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.350 to 26.369 min.: rxn_060307_050.D (-)
443
650000
600000
550000
500000
450000
400000
350000
300000
250000
71
200000
295
150000
100000
165
43
107127
50000
195
89
0
40
60
145
415
237
219
265
317
343
369
387
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 358 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.412 to 26.431 min.: rxn_060307_050.D (-)
443
130000
120000
110000
100000
90000
80000
70000
71
60000
50000
40000
30000
158
295
43
107
127
20000
179
10000
223
205
267
249
89
0
40
60
425
369
329
387
405
347
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.455 to 26.474 min.: rxn_060307_050.D (-)
429
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
71
80000
60000
181
43
40000
107
20000
89
0
40
60
295
153
135
209
267
230249
317337 359 383
411
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 359 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.540 to 26.564 min.: rxn_060307_050.D (-)
429
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000
71
181
43
91
135
117
295
163
0
40
60
209
237
317 343 365
383
401
265
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.607 to 26.630 min.: rxn_060307_050.D (-)
429
1000000
900000
800000
700000
600000
500000
400000
300000
200000
100000
71
181
43
295
107127 153
89
0
40
60
209
237
265
317 343
371
401
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 360 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.697 to 26.711 min.: rxn_060307_050.D (-)
550000
429
500000
450000
400000
350000
300000
250000
200000
71
150000
100000
43
50000
107127
153
209
89
0
40
60
295
181
237
265
331 357 381
399
313
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.787 to 26.811 min.: rxn_060307_050.D (-)
443
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
71
60000
40000
43
181
107127
20000
89
0
40
60
295
153
209
237
265
317338357
385
415
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 361 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.835 to 26.854 min.: rxn_060307_050.D (-)
429
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000
20000
43
181
71
295
127 153
107
208 230251 277
0
40
60
327
345 368
399
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 26.878 to 26.892 min.: rxn_060307_050.D (-)
429
450000
400000
350000
300000
250000
200000
150000
100000
50000
0
71
181
43
107
89
295
135
153
211 237
265
324343
371 398
448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 362 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 27.039 to 27.063 min.: rxn_060307_050.D (-)
443
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
71
5000
43
107
153
135
207
181
238
0
40
60
309
267 289
341
368
401
419
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 27.116 to 27.149 min.: rxn_060307_050.D (-)
443
60000
55000
50000
45000
40000
35000
30000
25000
20000
71
15000
181
43
10000
5000
0
107
89
135
153
295
200 223 247 274
313
343
415
373 396
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 363 -
UNKNOWN – impurity in or breakdown product of tris(nonylphenyl) phosphite
Abundance
Average of 29.474 to 29.684 min.: rxn_060307_050.D (-)
177
900000
800000
700000
600000
368
500000
400000
300000
217
200000
263
57
87
100000
121 147
236
199
0
281
312
350
330
401
429
447
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
Average of 16.116 to 16.268 min.: rxn_060307_051.D (-)
161
2200
2000
1800
1600
249
1400
1200
1000
800
600
400
133
207
91
200
73
53
282
115
179
40
60
341
304
323
0
401
371
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 364 -
UNKNOWN – impurity in or breakdown product of di-(2-ethylhexyl) phthalate
Abundance
Average of 16.882 to 17.024 min.: rxn_060307_051.D (-)
291
550
500
450
207
400
350
101
300
250
147
78
57
200
121
150
343
100
267
50
325
239
185
165
40
401
383
0
40
60
429
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of di (2-ethylhexyl) phthalate
Abundance
Average of 17.604 to 18.004 min.: rxn_060307_051.D (-)
149
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
177
15000
195
10000
70
5000
41
104
122
0
40
60
221
251
282 306327
355
387
415
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 365 -
DEHP ISOMER – impurity in or breakdown product of di-(2-ethylhexyl) phthalate
Abundance
Average of 20.391 to 20.463 min.: rxn_060307_051.D (-)
149
6000
5500
5000
4500
4000
3500
3000
2500
167
2000
1500
57
1000
113
500
279
415
76
94
0
40
60
195
131
223
251
328
311
357
385
441
80 100120140160180200220240260280300320340360380400420440
m/z-->
DEHP ISOMER – impurity in or breakdown product of di-(2-ethylhexyl) phthalate
Abundance
Average of 21.105 to 21.195 min.: rxn_060307_051.D (-)
149
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
167
18000
16000
14000
57
12000
10000
279
8000
113
6000
4000
83
2000
131
0
40
60
205
186
231251
311
342 365
399
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 366 -
DEHP – impurity in or breakdown product of di-(2-ethylhexyl) phthalate
Abundance
Average of 21.556 to 21.737 min.: rxn_060307_051.D (-)
149
3000000
167
2800000
2600000
2400000
2200000
2000000
1800000
279
1600000
57
1400000
1200000
1000000
800000
113
600000
83
400000
200000
261
221 242
203
185
0
40
60
304
334
361
391 416
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of N,Nbis(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-octylphenyl ether, n~5
Abundance
Average of 15.502 to 15.707 min.: rxn_120307_015.D (-)
179
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
135
25000
20000
15000
10000
107
57
5000
250
77
0
161
40
40
60
207
233
281
327
355
387
415
432
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 16.853 to 16.901 min.: rxn_120307_015.D (-)
235
4000
3500
3000
2500
2000
135
1500
1000
44
191
500
207
78
0
40
60
306
115
97
175
159
253
281
327
355
401
80 100120140160180200220240260280300320340360380400
m/z-->
- 368 -
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 16.991 to 17.024 min.: rxn_120307_015.D (-)
135
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
247
3000
2500
2000
1500
57
1000
107
500
179
161
77
40
318
209
0
40
60
281
341
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 17.200 to 17.243 min.: rxn_120307_015.D (-)
119
161
4500
4000
223
3500
3000
2500
45
2000
91
1500
1000
294
500
65
137
179
205
269
251
0
40
60
341
400
429
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
Average of 18.365 to 18.517 min.: rxn_120307_015.D (-)
223
220000
200000
180000
160000
140000
120000
100000
135
80000
60000
40000
45
20000
107
294
161
179 205
77
0
267
249
313
341
369387
415
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 18.879 to 18.912 min.: rxn_120307_015.D (-)
223
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
135
20000
18000
16000
14000
12000
10000
8000
6000
45
4000
107
2000
77
0
40
60
161
179
205
265
247
294
327
355
399
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 370 -
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 18.941 to 18.969 min.: rxn_120307_015.D (-)
57
4500
161
279
4000
3500
3000
217
2500
2000
350
119
1500
1000
91
500
191
136
247
74
40
60
401
311329
0
429
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 19.107 to 19.155 min.: rxn_120307_015.D (-)
291
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
57
10000
8000
6000
4000
247
175
2000
91
0
40
60
119
147
194
219
267
362
342
324
401
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 371 -
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 19.378 to 19.459 min.: rxn_120307_015.D (-)
279
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
191
2500
2000
1500
57
1000
350
136
500
75
0
40
60
161
95 115
210229249
297
328
371
401
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 19.749 to 19.792 min.: rxn_120307_015.D (-)
161
4000
3500
3000
119
45
2500
267
2000
1500
87
1000
500
338
207
69
181
139
237
0
40
60
292310
359
415
385
432
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-octylphenyl ether, n~5
Abundance
Average of 20.796 to 20.948 min.: rxn_060307_054.D (-)
267
11000
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
45
135
2500
2000
1500
89
1000
161
338
107
500
179
67
205
237
293313
0
40
60
402
358 383
429
446
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 21.266 to 21.390 min.: rxn_120307_015.D (-)
335
50000
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
57
16000
267
14000
12000
10000
8000
161
247
6000
135
406
4000
89
2000
189
107
217
0
40
60
295
317
356
387
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 373 -
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 22.931 to 23.102 min.: rxn_060307_054.D (-)
311
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
45
12000
10000
135
8000
89
6000
161
4000
382
107
2000
67
179
0
40
60
205
223
252
279
339358
418 441
400
80 100120140160180200220240260280300320340360380400420440
m/z-->
UNKNOWN – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 23.416 to 23.468 min.: rxn_120307_015.D (-)
379
30000
28000
26000
24000
22000
20000
18000
16000
14000
57
12000
10000
8000
6000
4000
2000
161
247
89
133
113
207
189
229
0
273
311
291
339
358
415435
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 374 -
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND - impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 24.938 to 24.999 min.: rxn_060307_054.D (-)
355
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
45
11000
10000
9000
8000
7000
6000
89
161
135
5000
4000
3000
2000
71
187
0
40
60
426
205
107
1000
223
241
259
311
289
337
384405
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n~5
Abundance
Average of 26.650 to 26.849 min.: rxn_120307_015.D (-)
399
75000
70000
65000
60000
55000
50000
45
45000
40000
35000
30000
89
161
25000
20000
135
15000
205
10000
5000
107
67
0
40
60
187
311
223 249
267 293
337
369
418 443
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
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n=9-10
Abundance
Average of 20.772 to 20.862 min.: rxn_120307_016.D (-)
267
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
135
45
4000
3000
89
2000
161
338
107
1000
67
179
205223
0
40
60
249
311
357
387
415
80 100120140160180200220240260280300320340360380400420
m/z-->
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n=9-10
Abundance
Average of 22.931 to 23.045 min.: rxn_120307_016.D (-)
311
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
45
20000
135
15000
89
161
10000
5000
382
107
67
0
40
60
179
205
223 249
267
285
339358
415
432
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 376 -
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n=9-10
Abundance
Average of 24.885 to 24.928 min.: rxn_120307_016.D (-)
355
140000
130000
120000
110000
100000
90000
80000
70000
45
60000
50000
40000
161
89
30000
135
20000
10000
40
60
426
205
107
67
223 249
267 293
179
0
325
397
378
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n=9-10
Abundance
Average of 26.645 to 26.711 min.: rxn_120307_016.D (-)
399
38000
36000
34000
32000
30000
28000
26000
45
24000
22000
20000
18000
16000
89
14000
161
12000
10000
135
8000
6000
205
4000
107
2000
67
187
223 249
0
40
60
297
277
326
369
345
419 441
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 377 -
2-(2-4(1,1,3,3-TETRAMETHYLBUTYL)PHENOXY)ETHOXY)
ETHANOL
LIKE
COMPOUND – impurity in or breakdown product of polyethylene glycol 4-tert-octylphenyl ether, n=9-10
Abundance
Average of 28.514 to 28.604 min.: rxn_120307_016.D (-)
45
4500
443
4000
3500
207
3000
89
161
2500
133
2000
1500
281
355
1000
249
500
415
107
325
179
67
381
299
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
Average of
850000
17.757 to 18.089 min.:
225
rxn_060307_055.D (-)
800000
750000
700000
650000
600000
550000
500000
450000
400000
350000
300000
93
250000
168
200000
65
150000
196
100000
50000
113
41
141
253
0
40
60
283
302
328
356
401
383
429
448
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-(2Hbenzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol were analysed by GCMS
2-(2H-BENZOTRIAZOLE-2-YL)-4,6-BIS(1-METHYL-1-PHENYLETHYL)PHENOL
Abundance
Average of 28.847 to 29.175 min.: rxn_060307_057.D (-)
432
1600000
1400000
1200000
1000000
800000
600000
342
400000
91
119
200000
41
65
0
165
141
207
189
228 252
281
314
370
406
388
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
Average of 8.317 to 8.497 min.: rxn_120307_021.D (-)
119
4000
3500
3000
2500
91
2000
1500
1000
500
176
56
73
147
207
0
40
60
251
281
341
401
429
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
Average of 6.091 to 6.148 min.: rxn_060307_011.D (-)
341
3000
2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
45
600
73
163
400
267
207
200
295
135
91
237
117
181
0
40
60
359
389
416
80 100120140160180200220240260280300320340360380400420
m/z-->
SILICIC ACID, DIETHYL BIS(1-METHYLSILYL) ESTER – impurity in or breakdown
product of dioctyltin bis(ethylmaleate)
Abundance
Average of 6.234 to 6.286 min.: rxn_060307_011.D (-)
207
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
237
6000
281
4000
2000
0
45
40
73
60
133
96 115
150
177
254
299
327
356
416
80 100120140160180200220240260280300320340360380400420
m/z-->
- 381 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 6.329 to 6.358 min.: rxn_060307_011.D (-)
341
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
73
163
500
193
54
295
221
133
98
269
252
0
40
60
415
313
358
385
80 100120140160180200220240260280300320340360380400420
m/z-->
DECAMETHYL CYCLOPETASILOXANE – impurity in or breakdown product of
dioctyltin bis(ethylmaleate)
Abundance
Average of 6.405 to 6.448 min.: rxn_060307_011.D (-)
355
5000
4500
4000
3500
73
267
3000
2500
2000
1500
1000
113
500
45
96
133
162
191
209
249
323
295
401
429
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
- 382 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 6.624 to 6.657 min.: rxn_060307_030.D (-)
237
267
2800
2600
2400
2200
2000
1800
1600
1400
1200
193
1000
137
800
155
600
355
400
119
200
211
78
46
295
96
327
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
Average of 7.000 to 7.090 min.: rxn_060307_011.D (-)
99
600000
550000
500000
450000
400000
350000
300000
250000
200000
127
150000
100000
54
50000
82
145
0
40
60
172
207
189
249
282
323341
371
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 383 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 7.637 to 7.694 min.: rxn_060307_030.D (-)
193
2000
237
1800
1600
1400
1200
1000
800
99
600
211
119
281
400
200
45
81
311
255
143 165
342
385
0
40
60
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average
of
7.841
to
7.874
1600
min.: rxn_060307_030.D
269
(-)
1500
1400
1300
1200
1100
1000
900
800
133
700
600
500
151
193
400
250
100
300
75
200
100
41
175
311
223
58
286
341
431
369
404
0
40
60
80 100120140160180200220240260280300320340360380400420
m/z-->
- 384 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 7.946 to 8.003 min.: rxn_060307_011.D (-)
415
2800
327
2600
2400
2200
2000
1800
1600
73
1400
1200
1000
800
600
399
400
99
200
45
127
147
179
208
225
295
268
251
355
0
40
60
80
100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 8.155 to 8.179 min.: rxn_060307_030.D (-)
193
4500
4000
3500
3000
237
2500
2000
1500
1000
279
500
40
63
89
135
115
163
353
211
0
40
60
297
326
401
431
80 100120140160180200220240260280300320340360380400420
m/z-->
- 385 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 8.293 to 8.331 min.: rxn_060307_030.D (-)
193
4000
3500
3000
237
2500
2000
1500
1000
133
500
163
45
74
279
105
210
0
40
60
254
297
342
325
369
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 8.616 to 8.664 min.: rxn_060307_011.D (-)
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
191
73
1000
103
55
0
40
60
80
133
165
223
297
325
415
399
100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->
- 386 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 10.756 to 10.790 min.: rxn_060307_011.D (-)
355
7500
7000
6500
6000
5500
73
5000
177
4500
4000
267
3500
3000
2500
2000
1500
325
1000
500
55
96
0
40
60
133
150
429
207
249
229
293
399
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 11.123 to 11.170 min.: rxn_060307_011.D (-)
161
16000
15000
14000
203
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
91
3000
41
115
134
2000
65
1000
185
0
40
60
220
237
265
293313
341
401
427
80 100120140160180200220240260280300320340360380400420
m/z-->
- 387 -
BUTYLATED HYDROXYTOLUENE – impurity in or breakdown product of dioctyltin
bis(ethylmaleate)
Abundance
Average of 11.517 to 11.565 min.: rxn_060307_011.D (-)
205
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
145
57
500000
81
177
105
127
223
0
40
60
267
295
313
341
387
415
441
80 100120140160180200220240260280300320340360380400420440
m/z-->
BRANCHED ALKANE – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 12.007 to 12.050 min.: rxn_060307_011.D (-)
3500
57
3000
2500
2000
85
1500
112
1000
140
500
207
161
0
189
268
226 249
295
328
355
387
415
443
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 388 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 12.178 to 12.240 min.: rxn_060307_011.D (-)
69
1600
1400
1200
1000
111
800
41
224
600
400
91
129
177
415
200
199
154
265
282
0
40
60
343
385
311
80 100120140160180200220240260280300320340360380400420
m/z-->
HEXADECANE – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 12.654 to 12.749 min.: rxn_060307_011.D (-)
57
14000
13000
12000
11000
10000
9000
85
8000
7000
6000
5000
4000
3000
2000
226
113
141
1000
40
0
40
177
197
159
60
341
251
282
323
429
401
383
80 100120140160180200220240260280300320340360380400420
m/z-->
- 389 -
1,1’-OXYBISBENZENE
–
impurity
in
or
breakdown
product
of
dioctyltin
bis(ethylmaleate)
Abundance
Average of 13.367 to 13.529 min.: rxn_060307_011.D (-)
71
30000
28000
26000
24000
22000
20000
18000
16000
14000
43
12000
10000
8000
112
6000
4000
2000
95
0
40
60
131
149
177
208
327
267
284 309
226 249
355
387
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 17.581 to 19.012 min.: rxn_060307_011.D (-)
207
16000
15000
14000
13000
12000
133
11000
10000
9000
8000
151
7000
281
6000
5000
4000
3000
73
2000
1000
96
45
115
177
225
0
40
60
341
251
309
359 383
415
439
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 390 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(ethylmaleate)
Abundance
Average of 19.768 to 20.272 min.: rxn_060307_011.D (-)
207
10500
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
325
1000
96
500
115
174
225
0
40
60
361
401
381
305
419 441
80 100120140160180200220240260280300320340360380400420440
m/z-->
Mass spectra of peaks detected when the solvent standards of dioctyltin bis(2ethylhexyl thioglycolate) were analysed by GC-MS
2-ETHYL-1-HEXANOL – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance
Average of 5.021 to 5.192 min.: rxn_060307_012.D (-)
57
450000
400000
350000
300000
250000
200000
150000
83
100000
50000
112
129147
40
0
40
60
177
207225
253
281
311
341
370
401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 391 -
2-ETHYLHEXYL MERCAPTOACETATE – impurity in or breakdown product of
dioctyltin bis(2-ethylhexyl thioglycolate)
Abundance
Average of 10.637 to 11.051 min.: rxn_060307_012.D (-)
190000
57
180000
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
112
50000
40000
30000
83
20000
145
10000
175
0
40
60
207
225
251
281
311
341
387
369
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
2,4-BIS(1,1-DIMETHYLETHYL)PHENOL – impurity in or breakdown product of
dioctyltin bis(2-ethylhexyl thioglycolate)
Abundance
Average of 11.532 to 11.570 min.: rxn_060307_012.D (-)
191
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000
2000
47
0
40
60
74 91
115
133
163
209
239
267285
325343
387
416
80 100120140160180200220240260280300320340360380400420
m/z-->
- 392 -
BRANCHED ALKANE – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance
Average of 11.584 to 11.608 min.: rxn_060307_012.D (-)
71
6500
6000
5500
5000
4500
43
4000
3500
3000
99
2500
182
2000
1500
1000
127
500
154
211
0
40
60
269
251
295
342
325
401
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
BRANCHED ALKANE – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance
Average of 11.788 to 11.850 min.: rxn_060307_012.D (-)
57
4500
4000
3500
85
3000
2500
2000
197
1500
1000
112
154
500
267
135
0
40
60
175
221
249
284
343
309
326
401
383
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 393 -
BRANCHED ALKANE – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance
Average of 11.979 to 12.050 min.: rxn_060307_012.D (-)
57
7500
7000
6500
6000
5500
5000
4500
4000
85
3500
3000
2500
112
2000
140
1500
1000
500
0
182
163
40
40
60
211
251
283
313
342
388
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance
Average of 12.178 to 12.231 min.: rxn_060307_012.D (-)
129
7000
73
6500
6000
5500
5000
4500
4000
3500
55
3000
199
2500
2000
1500
1000
500
0
97
149169
222
251
281
327
355
401
432
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 394 -
HEXADECANE – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance
Average
of
12.635
to
12.711
min.:
rxn_060307_012.D
(-)
57
105000
100000
95000
90000
85000
80000
75000
70000
65000
60000
55000
85
50000
45000
40000
35000
30000
25000
20000
15000
10000
113
226
141
5000
169
197
0
40
60
253
271 295
341
323
369
387
415
445
80 100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
m/z-->
1,1’-OXYBIS OCTANE LIKE COMPOUND – impurity in or breakdown product of
dioctyltin bis(2-ethylhexyl thioglycolate)
Abundance
Average of 13.377 to 13.453 min.: rxn_060307_012.D (-)
71
150000
140000
130000
120000
110000
100000
90000
80000
70000
43
60000
50000
40000
112
30000
20000
10000
95
0
40
60
131
157
185 209
241 265
282
341
369
415
397
80 100120140160180200220240260280300320340360380400420
m/z-->
- 395 -
UNKNOWN – impurity in or breakdown product of dioctyltin bis(2-ethylhexyl
thioglycolate)
Abundance
Average of 22.284 to 22.350 min.: rxn_060307_012.D (-)
57
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
164
10000
182
9000
8000
276
7000
406
6000
5000
112
4000
137
3000
83
2000
294
1000
204
222
0
40
60
250
342
325
361
387
430
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
Average of 16.806 to 16.958 min.: rxn_060307_032.D (-)
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
241
70
1500
1000
115
500
199
135
177
0
40
60
221
265
306
325
355
383
415
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 396 -
OCTADECANOIC ACID, ETHYL ESTER – impurity in or breakdown product of
epoxidised soya bean oil
Abundance
Average of 18.670 to 18.789 min.: rxn_060307_032.D (-)
88
4000
3500
3000
2500
2000
1500
43
312
1000
69
269
157
133
500
207
115
185
227 251
0
40 60
357
293
401
383
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
trans-9,10-EPOXYOCTADECANOIC ACID – impurity in or breakdown product of
epoxidised soya bean oil
Abundance
7000
55
Average of 20.125 to 20.220 min.: rxn_060307_032.D (-)
155
6500
6000
5500
5000
88
4500
4000
3500
3000
2500
109
2000
1500
1000
500
185
213
136
415
241 265
0
295
329
357
383
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 397 -
UNKNOWN – impurity in or breakdown product of epoxidised soya bean oil
Abundance
Average of 21.024 to 21.119 min.: rxn_060307_032.D (-)
130
3500
3000
2500
2000
1500
1000
371
239
43
101
429
71
500
149
315
194
176
221
259 284
343
401
448
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
EPOXIDISED FATTY ACID – impurity in or breakdown product of epoxidised soya
bean oil
Abundance
Average of 21.266 to 21.366 min.: rxn_060307_032.D (-)
155
11500
11000
10500
10000
9500
9000
55
8500
8000
7500
7000
6500
6000
5500
83
5000
4500
109
4000
3500
3000
2500
2000
1500
137
1000
194
500
175
0
40
60
213
239
265
295
322
357
403
385
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 398 -
EPOXIDISED FATTY ACID – impurity in or breakdown product of epoxidised soya
bean oil
Abundance
Average of 21.528 to 21.623 min.: rxn_060307_032.D (-)
155
4500
4000
3500
55
3000
2500
83
2000
1500
109
1000
221
265
500
137
175
356
201
239
295
385
328
417
0
40
60
446
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
Average of 17.923 to 18.223 min.: rxn_060307_033.D (-)
3200
60
3000
2800
2600
2400
256
2200
41
2000
129
1800
1600
213
1400
96
1200
1000
800
157
185
600
429
356
400
328
200
285
79
0
40
60
238
309
401
384
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 399 -
STEARIC ACID
Abundance
73
450000
Average of 18.660 to 18.974 min.: rxn_060307_033.D (-)
284
43
400000
350000
129
300000
241
250000
185
200000
97
150000
100000
50000
157
213
265
0
312
417
330 355 379399
447
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
Average of 17.624 to 17.647 min.: rxn_060307_034.D (-)
157
85000
80000
75000
231
185
70000
65000
60000
55000
50000
45000
40000
35000
30000
43
25000
129
20000
15000
10000
301
111
5000
61
85
213
0
40
60
273
253
329
355
401
383
430
80 100120140160180200220240260280300320340360380400420
m/z-->
- 400 -
BUTYL CITRATE – impurity in or breakdown product of acetyl tributyl citrate
Abundance
Average of 17.723 to 17.752 min.: rxn_060307_034.D (-)
185
6500
6000
5500
5000
4500
4000
3500
2500
2000
259
129
3000
157
43
1500
1000
231
301
283
327
111
500
87
67
207
0
40
60
356 379
415
80 100120140160180200220240260280300320340360380400420
m/z-->
UNKNOWN – impurity in or breakdown product of acetyl tributyl citrate
Abundance
Average of 17.852 to 17.909 min.: rxn_060307_015.D (-)
185
1400
1300
1200
1100
129
1000
900
41
800
245
700
600
500
400
157
273
300
327
200
112
58
100
203
87
221
0
40
60
415
356
295
385
80 100120140160180200220240260280300320340360380400420
m/z-->
- 401 -
1-PROPENE-1,2,3-TRICARBOXYLIC ACID, TRIBUTYL ESTER – impurity in or
breakdown product of acetyl tributyl citrate
Abundance
Average of 18.375 to 18.418 min.: rxn_060307_015.D (-)
112
157
170000
160000
150000
140000
130000
120000
110000
57
100000
139
90000
80000
70000
60000
213
50000
269
40000
30000
84
20000
185
241
10000
287
0
40
60
313
342
369
402
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
1-PROPENE-1,2,3-TRICARBOXYLIC ACID, TRIBUTYL ESTER – impurity in or
breakdown product of acetyl tributyl citrate
Abundance
Average of 18.503 to 18.575 min.: rxn_060307_015.D (-)
112
157
30000
28000
26000
24000
22000
20000
18000
57
139
16000
14000
12000
10000
213
8000
269
6000
4000
2000
84
185
241
287 313
0
342 369
402 429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 402 -
1-PROPENE-1,2,3-TRICARBOXYLIC ACID, TRIBUTYL ESTER – impurity in or
breakdown product of acetyl tributyl citrate
Abundance
Average of 18.637 to 18.817 min.: rxn_060307_015.D (-)
112
157
46000
44000
42000
40000
38000
36000
34000
32000
57
30000
28000
26000
139
24000
22000
20000
18000
185
16000
213
14000
12000
269
10000
8000
6000
84
4000
241
2000
287
0
40
60
313
342
371
401
431
80 100120140160180200220240260280300320340360380400420440
m/z-->
ATBC
Abundance
Average of 19.169 to 19.293 min.: rxn_060307_015.D (-)
185
7000000
6500000
259
6000000
5500000
129
5000000
4500000
4000000
3500000
3000000
2500000
43
2000000
157
1500000
329
1000000
111
500000
61
87
213
231
0
277
301
347 373
403 429
447
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
15
2000
1500
1000
27
19
500
3740
0
0
5
10
15
20
25
30
35
40
46
45
51
50
55
58
6568
55
65
60
73
70
7780 84
75
80
85
89
94
90
m/z-->
PP2
Abundance
Scan 392 (8.516 min): FSA_015.D (-386) (-)
115
4800
4600
4400
4200
4000
3800
3600
3400
3200
3000
2800
2600
2400
2200
59
2000
1800
1600
28
1400
1200
1000
800
600
400
201
200
150
267
299337
416
492
574
620656 696 735
0
0
50
100
150
200
250
300
350
m/z-->
- 407 -
400
450
500
550
600
650
700
PP3
Abundance
Scan 515 (9.593 min): FSA_015.D (-510) (-)
91
120
5500
5000
4500
4000
3500
3000
2500
2000
65
1500
1000
29
500
51
39
74
84
17
0
0
10
20
30
40
50
60
70
80
104 113
90
150
128 136
100 110 120 130 140
m/z-->
PP4
Abundance
Scan 584 (10.197 min): FSA_015.D (-580) (-)
140
4200
83
4000
3800
3600
3400
3200
3000
2800
2600
2400
42
2200
2000
1800
1600
1400
1200
1000
800
600
400
191229
200
274
329
389
421
474509
551 593628
681
0
0
50
100
150
200
250
300
350
m/z-->
- 408 -
400
450
500
550
600
650
700
739
PP5
Abundance
Scan
70
1027
(13.929
min):
FSA_199.D
(-1035)
(-)
3000
2800
2600
43
2400
168
2200
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
161
46000
(15.365
min):
FSA_199.D
(-1186)
(-)
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
0
0
50
100
150
200
250
716
506
300
350
m/z-->
- 409 -
400
450
500
550
600
650
700
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
57
10000
206
91
115
41
5000
77
28
15
179
128
67
0
0
105
20
40
60
147
163
138
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
248
297
371
423
486
621
552588
729 771
0
0
50
100
150
200
250
300
350
400
m/z-->
- 410 -
450
500
550
600
650
700
750
PP9
Abundance
Scan 1609 (19.025 min): FSA_199.D (-1604) (-)
88
40000
35000
30000
101
25000
20000
15000
10000
73
61
5000
29
157
45
115
213
129 143
171
17
0
20
40
60
80
100
120
140
160
185 199
180
200
227 241 256
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
295
327
495
402
563
614
766
670
0
0
50
100
150
200
250
300
350
400
m/z-->
- 411 -
450
500
550
600
650
700
750
PP11
Abundance
Scan 1775 (20.625 min): FSA_015.D (-1771) (-)
277
24000
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
0
463
429
313 355
0
50
100
150
200
250
300
350
400
450
717
538579
500
550
600
650
700
767
750
800
m/z-->
PP12
Abundance
Scan 1812 (20.802 min): FSA_199.D
150000
43
140000
130000
57
120000
110000
73
100000
90000
80000
70000
60000
50000
85
29
40000
30000
129
97
111
20000
10000
143
15
0
20
40
60
80
100
120
m/z-->
- 412 -
140
213
157171185
256
199
227
239
270
160
180
200
220
240
260
PP13
Abundance
Average of 21.238 to 21.247 min.: FSA_015.D (-)
147
16000
15000
291
14000
13000
12000
11000
10000
9000
8000
57
7000
219
6000
5000
4000
91
3000
187
2000
1000
0
19
0
348383 430468504 549
251
50
100
150
200
250
300
350
400
450
500
550
612
600
681716755
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
40000
97
30000
111
185
20000
284
241
171
143
157
10000
15
20
40
60
80
100
120
140
m/z-->
- 413 -
160
180
199
213227
200
220
240
255269
260
280
PP15
Abundance
Scan 2056 (23.085 min): FSA_015.D
88
70000
60000
50000
40000
30000
43
20000
29
69
157
10000
102
15
0
0
20
40
60
80
143
129
269
199213227241255
171185
283
312
100 120 140 160 180 200 220 240 260 280 300
m/z-->
PP16
Abundance
Scan 2090 (23.236 min): FSA_199.D (-2099) (-)
168
140000
120000
70
100000
80000
60000
284
102
40000
41
20000
138
200227255
0
0
50
100
150
200
250
319 357
300
m/z-->
- 414 -
350
415
400
509
450
500
624
550
600
PP17
Abundance
Scan 2105 (23.514 min):
170
5600
FSA_015.D (-2101) (-)
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
216
600
400
248
356
386
421
451
200
520
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
84
8000
239
116
6000
4000
29
2000
137 154
182
196
211
168
225
15
0
0
20
40
60
80
281
267
253
312
333
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
57
34000
32000
30000
28000
26000
24000
22000
20000
18000
129
98
16000
14000
12000
10000
8000
6000
185
4000
18
2000
239
283
341
374
404
0
0
50
100
150
200
250
300
350
400
473
450
500
568
550
698
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
18
250
342
403
464
526
591
683
736 784
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
98
9000
8000
74
7000
211
6000
57
5000
134
4000
29
112
3000
2000
229
154
1000
16
168
271
242
185
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
207
109
262
433
200
298
355
471
525
574 617
662
711
754 795
0
0
50
100
150
200
250
300
350
400
m/z-->
- 417 -
450
500
550
600
650
700
750
800
PP23
Abundance
Scan 2242 (24.567 min): FSA_199.D (-2249) (-)
59
70000
65000
60000
55000
50000
45000
40000
35000
30000
72
25000
20000
43
15000
10000
86
5000
29
0
10
20
114
128
100
18
30
40
50
60
70
80
142
156
170
184
198
90 100110120130140150160170180190
m/z-->
PP24
Abundance
Scan 2247 (24.611 min): FSA_199.D (-2241) (-)
88
30000
25000
20000
15000
55
10000
157
29
5000
115
0
0
213
186
50
100
150
200
297
255
250
m/z-->
- 418 -
300
340
364
350
400 429 461
400
450
536
500
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
0
0
50
551
610646
730766
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
101
3000
83
2000
147
27
1000
160
203
178
219
239
267
313
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
74
300000
250000
239
200000
150000
167
100000
116
50000
257
27
0
20
40
299
182
58
131
213
197
0
60
283
315
343
366
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
43
2200
2000
1800
1600
1400
1200
1000
114
800
600
155
191
223
400
200
292327
253
388
428
483 523
623
684
0
0
50
100
150
200
250
300
350
m/z-->
- 420 -
400
450
500
550
600
650
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
313
18
200
431
520
358
217
398
469
568605
647 687
739
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
58
5000
4500
4000
3500
3000
2500
141
2000
1500
237
1000
178
500
0
16
0
50
282
343
383 429 475
551589 634
781
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
548586
639
714
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
117
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
43
15000
101
10000
75
59
5000
133
148
28
190
171
0
0
20
40
60
80
207
259
223 241
341
281
299
325
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
285
154
50000
27
185
169
0
0
20
40
60
80
210
327
241
225
311
342359
100 120 140 160 180 200 220 240 260 280 300 320 340 360
m/z-->
PP34
Abundance
Average of 27.734 to 27.778 min.: FSA_015.D (-)
59
450000
400000
350000
300000
250000
200000
150000
100000
97
50000
140
18
184
0
0
50
240
294 337
371 415 461 504
540
609647684
749785
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
43
6000
4000
114 128
86 101
29
2000
147
194 209
170
221
158
182
18
0
0
20
40
60
80
100
120
140
160
180
200
220
240
251263
240
m/z-->
PP36
Abundance
Scan 2614 (27.971 min): FSA_015.D (-2619) (-)
69
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
207
1500
341
130
1000
32
500
162
254
298
387 430
490
0
0
50
100
150
200
250
300
350
400
m/z-->
- 424 -
450
500
542
550
669
595
634
718
600
650
700
774
750
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
1500
152
28
208
1000
414
452 501
355
315
500
245
595 639 681
561
0
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
767
750
m/z-->
PP38
Abundance
Scan 2703 (28.750 min): FSA_015.D (-2699) (-)
98
7000
6500
43
6000
5500
5000
4500
4000
134
3500
3000
2500
2000
295
193
1500
1000
238
500
356
430
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
141
201
299
0
0
50
100
150
200
250
300
384
415
474507
445
350
400
450
500
565
550
610
600
660
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
43
70000
60000
50000
40000
83
30000
20000
126
109
10000
27
154
170 191
207226
0
0
20
40
60
80
322
249267285 305
364
348
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) (-)
59
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
112
193
1500
341
1000
429
18
500
149
237
282
475 524
558
383
623
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 281313
341
368 401
0
0
50
100
150
200
250
300
m/z-->
- 427 -
350
400
445
450
489
500
550
577 611
550
600
PP43
Abundance
Scan 2847 (29.864 min): FSA_199.D (-2839) (-)
152
50000
45000
40000
35000
30000
25000
70
20000
43
434
15000
10000
123
5000
311
222
190
264
342373
400
0
50
100
150
200
250
300
350
462
400
450
505536
563597
500
550
600
655
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
27
283
95
0
0
50
100
150
200
250
300
388
357
350
m/z-->
- 428 -
400
459
450
504
500
550585 623
550
600
650
698
700
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
5000
131
247 281312341
368 403
0
0
50
446
219
30
10000
100
150
200
250
300
350
400
475503
450
549
500
550
604 639
600
m/z-->
PP46
Abundance
Scan 2732 (28.858 min): FSA_091.D (-2725) (-)
219
9000
8500
8000
7500
7000
57
6500
6000
163
5500
5000
4500
4000
3500
3000
2500
494
2000
129
1500
1000
281
500
0
429
91
341
25
50
100
150
200
250
300
386
350
400
m/z-->
- 429 -
549
461
450
500
550
609
600
755
650
700
750
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
441
91
590
1000
0
159
57
500
220
315
20
0
50
669708 756
475510 551
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
500000
191
91
0
308
273
15
0
646
237
50
100
150 200
250
300
385
345
350 400
m/z-->
- 430 -
503 549589
450
500
550 600
681
650
738 786
700
750 800
PP49
Abundance
Scan 3173 (32.865 min): FSA_015.D
57
120000
110000
100000
90000
80000
70000
60000
191
50000
647
316
147
40000
30000
20000
91
253
10000
0
355
15
0
50
100
150
200
250
300
350
401
443
479
400
450
535
500
575
611
550
600
679
650
728
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
209
10000
167
5000
275
15
0
388
427
353
239
0
50
100
150
200
250
300
350
m/z-->
- 431 -
400
450
498
500
540
550
598
600
653689 732
650
700
PP51
Abundance
Scan 3444 (35.091 min): FSA_199.D (-3453) (-)
119
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
73
2000
1500
191
1000
267
341
27
500
152
236
429
387
307
549
490
0
0
50
100
150
200
250
300
350
400
450
500
550
637671
604
600
650
729
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
152
1500
1000
341
223
500
18
185
403
476 517
581
0
0
50
100
150
200
250
300
350
m/z-->
- 432 -
400
450
500
550
624
600
650
708
700
758
750
PP53
Abundance
Scan 3605 (36.647 min): FSA_015.D (-3585) (-)
239
2400
2200
2000
1800
1600
74
1400
43
1200
191
1000
313
148
800
105
600
282
503
383
400
447
637
549
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
500
185
18
282
320 369
402
443
491
638
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
356
1000
431
148
500
277
389
476
18
551
518
591 638 687 727
786
0
0
50
100
150
200
250
300
350
400
m/z-->
- 434 -
450
500
550
600
650
700
750
Overlay of chromatograms (upper, green = PP + additives, red = PP) and EI
spectra (lowest one = PP + additives) of additional peaks observed with GCxGCTOF-MS in concentrated ethanol extract of PP + additives.
Codes correspond to Table 23 in the main report
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
Codes correspond to Table 19 in the main report
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
225
261281
166185 207
243
0
40
60
313 336356377
405
424 449
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE2
Abundance
Average of 6.624 to 6.662 min.: RXN_LSCREEN_060207_023.D (-)
57
65000
60000
55000
50000
45000
40000
35000
30000
98
25000
20000
15000
10000
5000
79
124
159
0
40
60
191
208
237
267
285306
341
369 394415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 458 -
HDPE3
Abundance
Average of 9.197 to 9.216 min.: RXN_LSCREEN_060207_023.D (-)
56
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
83
15000
10000
182
111
5000
154
205
130
0
40
60
235
267286 307
339
372 395 417436
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE4
Abundance
Average of 9.297 to 9.325 min.: RXN_LSCREEN_060207_023.D (-)
55
85000
80000
75000
70000
83
65000
60000
55000
135
50000
45000
40000
35000
30000
25000
111
20000
15000
10000
154
5000
182
205
0
40
60
259 282 303323
241
342 364
397
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 459 -
HDPE5
Abundance
240000
Average of 9.415 to 9.430 min.: RXN_LSCREEN_060207_023.D (-)
57
220000
200000
180000
160000
140000
120000
100000
85
80000
60000
40000
20000
112
184
141
0
165
205
242 265
294
341
372
401
431
449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE6
Abundance
30000
28000
Average of 9.525 to 9.549 min.: RXN_LSCREEN_060207_023.D (-)
43
71
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000
96
126
163
2000
0
145
194 217
235
281
263
299321343 367387
415
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 460 -
HDPE7
Abundance
Average of 11.242 to 11.265 min.: RXN_LSCREEN_060207_023.D (-)
81
200000
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
0
40
60
259 281301
319339
387
414
440
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE8
Abundance
600000
Average of 11.275 to 11.299 min.: RXN_LSCREEN_060207_023.D (-)
82
550000
500000
450000
400000
100
350000
300000
57
250000
200000
150000
100000
142
124
50000
167 189 213234 259 281 305
0
40
60
341
376 400
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 461 -
HDPE9
Abundance
Average of 11.341 to 11.365 min.: RXN_LSCREEN_060207_023.D (-)
86
1300000
1200000
57
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
200000
110
128
100000
156
198 221 245
180
263
281
0
40
60
311
341
358
388
427
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE10
Abundance
Average of 11.513 to 11.541 min.: RXN_LSCREEN_060207_023.D (-)
72
2800000
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
43
600000
400000
200000
95
0
40
60
142
165
124
193
221
249
281
299
327
355
383
415
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 462 -
HDPE11
Abundance
Average of 11.632 to 11.660 min.: RXN_LSCREEN_060207_023.D (-)
58
2800000
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
41
600000
400000
140
81
200000
109
0
40
60
157177 198 220240
265
282
309
341
387
412
439
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE12
Abundance
Average of 12.017 to 12.045 min.: RXN_LSCREEN_060207_023.D (-)
57
4000000
3500000
3000000
2500000
85
2000000
1500000
1000000
500000
113
212
141
0
40
60
169
193
233
263
282 307
325
343363383
415435
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 463 -
HDPE13
Abundance
Average of 12.121 to 12.174 min.: RXN_LSCREEN_060207_023.D (-)
191
8000000
7500000
7000000
6500000
6000000
5500000
5000000
57
4500000
4000000
3500000
3000000
163
2500000
91
2000000
115
1500000
1000000
133
500000
209 233 259 282
300
318 341 366
0
401420439
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE14
Abundance
Average of 12.197 to 12.216 min.: RXN_LSCREEN_060207_023.D (-)
82
700000
650000
43
600000
550000
500000
450000
400000
350000
300000
250000
200000
110
150000
154
100000
50000
61
0
40
60
180
198 220
253
282
309
341
367387
415 436
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 464 -
HDPE15
Abundance
120000
Average of 13.719 to 13.748 min.: RXN_LSCREEN_060207_023.D (-)
100
110000
100000
90000
80000
70000
60000
50000
40000
30000
57
20000
170
10000
123
152
197 223
259 281 307327
241
344363 385
403 429
446
75
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE16
Abundance
450000
Average of 13.795 to 13.810 min.: RXN_LSCREEN_060207_023.D (-)
86
400000
350000
57
300000
250000
200000
150000
100000
50000
0
110
40
40
138156
184
206226 252
281
309
327
356
385
440
60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 465 -
HDPE17
Abundance
Average of 13.957 to 13.981 min.: RXN_LSCREEN_060207_023.D (-)
72
900000
800000
700000
600000
500000
400000
300000
43
200000
100000
95
123
0
40
60
170
152
197
226245263283 307327
355
385404
435
80 100120140160180200220240260280300320340360380400420
m/z-->
HDPE18
Abundance
Average of 14.062 to 14.100 min.: RXN_LSCREEN_060207_023.D (-)
58
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
200000
100000
81
168
109
127 151
0
40
60
226
191
209
259 283 307
325
355
387
417
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 466 -
HDPE19
Abundance
Average of 14.371 to 14.414 min.: RXN_LSCREEN_060207_023.D (-)
57
5500000
5000000
4500000
4000000
3500000
85
3000000
2500000
2000000
1500000
1000000
113
240
500000
141
169
197
219
0
40
60
259 283
313
341
380 402
420
438
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE20
Abundance
Average of 14.556 to 14.580 min.: RXN_LSCREEN_060207_023.D (-)
57
360000
340000
320000
82
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
110
60000
40000
182
138
20000
208
160
0
40
60
238259 281 304 327
356
383
415
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 467 -
HDPE21
Abundance
Average of 15.027 to 15.055 min.: RXN_LSCREEN_160207_029.D (-)
55
70000
65000
60000
55000
50000
45000
40000
88
35000
191
30000
25000
166
20000
15000
209
124
10000
254
5000
147
106
0
40
60
281
230
311
341
385
367
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE22
Abundance
Average of 15.793 to 15.835 min.: RXN_LSCREEN_060207_023.D (-)
86
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000
56
20000
10000
113
0
40
60
152173193
224
254
290
272
321
355
384 408429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 468 -
HDPE23
Abundance
Average of 15.902 to 15.926 min.: RXN_LSCREEN_160207_029.D (-)
88
65000
60000
55000
50000
45000
40000
35000
30000
149
41
25000
69
20000
213
15000
10000
111
5000
129
270
185
167
241
289309
0
40
60
341
387
369
415
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE24
Abundance
Average of 16.068 to 16.102 min.: RXN_LSCREEN_060207_023.D (-)
86
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
56
50000
149
112131
0
40
60
183
201 224
254
299
281
317 341
372392 415
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 469 -
HDPE25
Abundance
Average of 16.511 to 16.539 min.: RXN_LSCREEN_060207_023.D (-)
100
170000
43
160000
150000
140000
130000
120000
110000
100000
90000
71
80000
70000
60000
50000
124
40000
30000
194
20000
152
10000
170
211
236
0
40
60
268
289 314
341 363
396 420 445
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE26
Abundance
2400000
Average of 16.820 to 16.839 min.: RXN_LSCREEN_060207_023.D (-)
277
2200000
2000000
1800000
1600000
1400000
1200000
1000000
57
800000
147
600000
219
400000
200000
91
128
109
185
253
166
295
0
40
60
327
355
385
415
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 470 -
HDPE27
Abundance
Average of 17.909 to 17.937 min.: RXN_LSCREEN_060207_023.D (-)
174
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000
59
120000
100000
80000
60000
40000
130
41
328
20000
77
0
40
60
98
156
198 224
280
242
298
261
356
389
408429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE28
Abundance
Average of 17.866 to 17.885 min.: RXN_LSCREEN_160207_029.D (-)
88
280000
260000
240000
220000
200000
180000
160000
140000
120000
57
100000
80000
298
157
60000
255
40000
213
111
20000
129
185
235
0
40
60
278
401
359 383
419
319 341
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 471 -
HDPE29
Abundance
Average of 17.914 to 17.937 min.: RXN_LSCREEN_160207_029.D (-)
55
160000
150000
140000
130000
120000
110000
83
100000
174
90000
250
80000
70000
60000
208
110
50000
40000
155
137
30000
296
20000
401
10000
328
232
355
373
268
0
40
60
429448
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE30
Abundance
Average of 17.985 to 17.999 min.: RXN_LSCREEN_060207_023.D (-)
174
500000
450000
400000
350000
300000
250000
200000
55
150000
98
100000
130
50000
208
151
253
328
79
228
0
40
60
284 309
357 380 403
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 472 -
HDPE31
Abundance
240000
Average of 18.023 to 18.047 min.: RXN_LSCREEN_060207_023.D (-)
116
220000
59
200000
180000
160000
140000
120000
100000
80000
60000
40000
86
20000
198
143 170
0
256
235
277
217
308329 355
390
429449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE32
Abundance
43
650000
Average of 18.099 to 18.113 min.: RXN_LSCREEN_060207_023.D (-)
211
98
600000
118
550000
500000
450000
400000
74
350000
242
300000
250000
200000
143
150000
100000
185
50000
167
271 296317 339
357
0
40
60
390
416
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 473 -
HDPE33
Abundance
Average of 18.147 to 18.175 min.: RXN_LSCREEN_060207_023.D (-)
174
800000
750000
700000
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
211
150000
130
100000
254
60
328
50000
229
89
156
0
40
60
280300
193
346 371392 417438
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE34
Abundance
Average of 18.285 to 18.299 min.: RXN_LSCREEN_060207_023.D (-)
174
160000
150000
140000
130000
59
120000
110000
100000
90000
80000
70000
60000
115
50000
136
40000
97
30000
20000
328
41
220
79
192
10000
155
248
0
40
60
281
300
357
386
415
442
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 474 -
HDPE35
Abundance
900000
Average of 18.332 to 18.346 min.: RXN_LSCREEN_060207_023.D (-)
118
800000
700000
600000
500000
400000
300000
256
200000
88
100000
136
55
164
192
220
0
278
311
343
371
401
429
446
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE36
Abundance
Average of 18.375 to 18.394 min.: RXN_LSCREEN_060207_023.D (-)
55
340000
83
320000
300000
280000
260000
240000
220000
200000
180000
160000
111
140000
120000
100000
80000
60000
136
40000
20000
164
213
234
192
263
281
299
0
40
60
329 355
386
415
446
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 475 -
HDPE37
Abundance
1800000
Average of 18.494 to 18.513 min.: RXN_LSCREEN_060207_023.D (-)
174
1600000
1400000
1200000
1000000
800000
600000
400000
130
200000
0
328
41 59
89 108
156
200 224
256
284306
346 371
389 414
442
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE38
Abundance
Average of 18.836 to 18.860 min.: RXN_LSCREEN_060207_023.D (-)
174
6000000
5500000
5000000
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
130
328
500000
43
88
69
0
40
60
112
155
281
200 224
242262
300
346
371
389
415
441
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 476 -
HDPE39
Abundance
Average of 18.893 to 18.908 min.: RXN_LSCREEN_060207_023.D (-)
118
3500000
3000000
2500000
2000000
256
1500000
1000000
43
74
500000
97
0
154
136
286 308327
224
184
356
384
414
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE40
Abundance
Average of 19.055 to 19.074 min.: RXN_LSCREEN_060207_023.D (-)
55
380000
360000
340000
83
320000
300000
280000
260000
240000
220000
200000
180000
160000
281
111
140000
120000
100000
80000
60000
137
40000
155
222
180
20000
199
246
0
40
60
310
343363
381402
429
446
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 477 -
HDPE41 (co-eluting)
Abundance
Average of 19.145 to 19.183 min.: RXN_LSCREEN_060207_023.D (-)
59
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
126
81
200000
253
100
41
0
40
60
210
154
192
174
235
281
310
328
346366
384
402
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE41 (co-eluting)
Abundance
Average of 19.198 to 19.245 min.: RXN_LSCREEN_060207_023.D (-)
256
6000000
74
5500000
118
5000000
4500000
4000000
3500000
3000000
43
2500000
2000000
1500000
284
1000000
185
500000
98
224
154
206
0
40
60
319 342
360 382
415 440
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 478 -
HDPE42
Abundance
2200000
Average of 19.003 to 19.022 min.: RXN_LSCREEN_160207_029.D (-)
59
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
41
86
200000
128
40
60
212
255
170
191
104
0
232
281
312 337
355
374 401
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE43
Abundance
8000000
Average of 19.416 to 19.445 min.: RXN_LSCREEN_060207_023.D (-)
85
57
7500000
7000000
6500000
6000000
5500000
5000000
4500000
113
4000000
3500000
3000000
2500000
141
310
2000000
169
1500000
1000000
197
225
500000
253
281
328 355
0
386405 429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 479 -
HDPE44
Abundance
30000
Average of 19.288 to 19.302 min.: RXN_LSCREEN_160207_029.D (-)
55
97
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
125
308
6000
4000
153
2000
75
281
182 208
248
0
342
387
368
415
449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE45
Abundance
Average of 19.588 to 19.616 min.: RXN_LSCREEN_060207_023.D (-)
118
1800000
1600000
1400000
1200000
256
1000000
800000
600000
400000
74
200000
56
0
100
140160 182
200 224
286 310330 355
390 415436
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 480 -
HDPE46
Abundance
Average of 19.668 to 19.687 min.: RXN_LSCREEN_060207_023.D (-)
174
1500000
1400000
1300000
1200000
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
328
118
200000
100000
43
75
224
146
100
40
60
256
276 298
200
0
356
382402
429
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE47
Abundance
Average of 19.754 to 19.811 min.: RXN_LSCREEN_060207_023.D (-)
55
800000
750000
700000
650000
600000
98
550000
500000
450000
236
400000
350000
300000
250000
179
200000
137
150000
79
100000
272
207
50000
312
155
119
294
0
40
60
334 357 382
401
430
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 481 -
HDPE48
Abundance
Average of 19.816 to 19.849 min.: RXN_LSCREEN_060207_023.D (-)
237
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
72
30000
25000
20000
15000
116
10000
5000
0
188
50
40
60
263
281300
160
322 344
370
402
430
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE49
Abundance
7000000
Average of 19.920 to 19.930 min.: RXN_LSCREEN_060207_023.D (-)
256
6500000
6000000
88
5500000
5000000
4500000
4000000
3500000
118
3000000
2500000
2000000
43
1500000
1000000
500000
0
69
140
168
186
212
230
286
309330 357 384
402 429447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 482 -
HDPE50
Abundance
Average of 19.944 to 19.959 min.: RXN_LSCREEN_060207_023.D (-)
256
1300000
1200000
1100000
98
1000000
900000
800000
58
700000
600000
500000
400000
300000
131
200000
227
154
100000
185
79
209
0
40
60
275 299 324
356
382402
421 445
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE51
Abundance
Average of 20.177 to 20.206 min.: RXN_LSCREEN_060207_023.D (-)
181
650000
600000
256
550000
500000
450000
400000
350000
300000
250000
200000
116
91
150000
100000
50000
41
65
152
134
0
40
60
202 226
274
295
313333 356 382 404
422443
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 483 -
HDPE52
Abundance
1100000
Average of 20.615 to 20.639 min.: RXN_LSCREEN_060207_023.D (-)
174
1000000
900000
800000
700000
600000
500000
400000
118
300000
55
200000
284
100
0
40
60
356
250
81
100000
137
155
207
326
307
232
374395
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE53
Abundance
Average of 20.567 to 20.605 min.: RXN_LSCREEN_160207_029.D (-)
59
4000000
3500000
3000000
2500000
2000000
1500000
41
1000000
83
126
500000
281
154
101
184 207
238
0
40 60
263
309
341
369
387
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 484 -
HDPE54
Abundance
8000000
Average of 20.848 to 21.005 min.: RXN_LSCREEN_060207_023.D (-)
59
7500000
7000000
6500000
6000000
5500000
5000000
41
4500000
4000000
3500000
3000000
2500000
126
81
2000000
1500000
281
100
1000000
256
154
238
184
500000
220
202
0
309
340359380
398
430449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE55
Abundance
Average of 21.043 to 21.119 min.: RXN_LSCREEN_060207_023.D (-)
57
5500000
5000000
85
4500000
4000000
118
3500000
3000000
284
2500000
2000000
1500000
1000000
141
338
169
500000
197
225
253
309
0
40
60
356376
404 429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 485 -
HDPE56
Abundance
Average of 21.433 to 21.499 min.: RXN_LSCREEN_060207_023.D (-)
55
5000000
4500000
264
98
4000000
3500000
3000000
2500000
2000000
1500000
137
79
1000000
221
165
500000
340
193
119
246
296
0
40
60
322
371 396
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE57
Abundance
Average of 21.637 to 21.652 min.: RXN_LSCREEN_060207_023.D (-)
118
400000
350000
300000
250000
284
200000
150000
74
100000
50000
44
0
100
154
187
255
210
229
314 336
354 382401 429449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 486 -
HDPE58
Abundance
Average
of
105000
21.685
129
to
21.709
min.:
RXN_LSCREEN_060207_023.D
(-)
100000
95000
90000
85000
80000
75000
70000
256
65000
60000
284
55000
50000
45000
40000
35000
30000
25000
185
20000
88
15000
10000
337
239
57
155
5000
312
203
106
0
40
60
371
398
431
449
80 100
120140160
180200220240
260280300320
340360380
400420440
m/z-->
HDPE59
Abundance
Average of 21.799 to 21.823 min.: RXN_LSCREEN_060207_023.D (-)
256
1800000
1600000
1400000
1200000
1000000
300
800000
600000
400000
200000
88
162
45
132
70
0
112
224
182
200
274
330
361 384404
423
441
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 487 -
HDPE60
Abundance
2000000
Average of 21.851 to 21.875 min.: RXN_LSCREEN_060207_023.D (-)
284
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000
57
88
0
118
139 161
252
196216
234
314 340
358 382404 430
448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE61
Abundance
280000
Average of 21.899 to 21.918 min.: RXN_LSCREEN_060207_023.D (-)
57
260000
240000
220000
200000
180000
85
160000
140000
337
120000
100000
80000
60000
40000
113
141
20000
169
308
210
238
189
0
40
60
261280
371 395415
432
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 488 -
HDPE62
Abundance
Average of 22.313 to 22.322 min.: RXN_LSCREEN_060207_023.D (-)
96
75000
70000
65000
55
60000
55000
50000
45000
40000
35000
30000
25000
362
20000
123
300
15000
10000
222
152
194
5000
250272
74
170
0
40
60
343
325
386 408429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE63
Abundance
Average of 23.016 to 23.045 min.: RXN_LSCREEN_060207_023.D (-)
131
600000
550000
500000
450000
400000
350000
300000
250000
55
200000
150000
101
100000
83
203
50000
236
151
179
60
412
292
316 341
0
40
264
369 392
430
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 489 -
HDPE64
Abundance
Average of 23.487 to 23.558 min.: RXN_LSCREEN_060207_023.D (-)
55
3200000
264
3000000
2800000
2600000
98
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
137
800000
79
600000
221
166
400000
325
119
200000
193
246
307
285
356
382
0
40
60
412
431
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE65
Abundance
38000
Average of 24.595 to 24.624 min.: RXN_LSCREEN_060207_023.D (-)
368
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
105
43
14000
12000
255
10000
71
159
314
8000
213
131
6000
4000
185
2000
393
282
234
339
411
440
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 490 -
HDPE66
Abundance
300000
Average of 24.833 to 24.866 min.: RXN_LSCREEN_060207_023.D (-)
368
280000
260000
240000
220000
200000
180000
160000
140000
147
120000
81
43
105
100000
80000
247
60000
213
40000
129
171
20000
40
60
326
191
63
0
283
301
350
393 415
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE67
Abundance
Average of 26.012 to 26.031 min.: RXN_LSCREEN_060207_023.D (-)
282
329
80000
254
75000
70000
65000
60000
55000
57
50000
45000
40000
35000
30000
441
25000
147
20000
15000
10000
91
5000
191
119
168
219
0
40
60
310
356 379399
417
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 491 -
HDPE68
Abundance
Average of 26.602 to 26.626 min.: RXN_LSCREEN_060207_023.D (-)
254
95000
90000
282
85000
80000
75000
70000
65000
60000
55000
50000
45000
347
40000
35000
30000
25000
20000
15000
10000
91
5000
147
117
40
72
427
191
219
168
300
0
40
60
327
371
396
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE69
Abundance
110000
Average of 27.063 to 27.097 min.: RXN_LSCREEN_060207_023.D (-)
385
100000
90000
441
80000
70000
57
60000
50000
40000
30000
91
147
280
20000
10000
191
117
165
0
237
219
257
329
355
310
410
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 492 -
HDPE70
Abundance
Average of 27.705 to 27.743 min.: RXN_LSCREEN_060207_023.D (-)
385
42000
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
339
109
2000
175
219
241
295
313
367
417
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE71
Abundance
120000
Average of 27.853 to 27.881 min.: RXN_LSCREEN_060207_023.D (-)
57
110000
100000
90000
80000
70000
60000
50000
449
85
40000
30000
20000
113
10000
0
141
282
207
169
225
187
253
326
308
344365
421
399
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 493 -
HDPE72
Abundance
120000
Average of 28.186 to 28.262 min.: RXN_LSCREEN_060207_023.D (-)
328
110000
100000
90000
80000
70000
60000
50000
40000
256
30000
20000
43
10000
69
88
160
118 142
183
0
212
238
298
279
348369
398 426 449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE73
Abundance
105000
Average of 28.861 to 28.913 min.: RXN_LSCREEN_060207_023.D (-)
256
100000
95000
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
43
328
20000
238
15000
88
10000
69
5000
118
140
40
60
298
212
169
191
276
0
356
380
398
433
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 494 -
HDPE74
Abundance
4000000
Average of 29.665 to 29.879 min.: RXN_LSCREEN_060207_023.D (-)
57
219
3500000
3000000
2500000
2000000
1500000
147
278
1000000
83
189
500000
107 129
167
247
0
317
297
345
374
402
431
449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE75
Abundance
Average of 29.959 to 30.031 min.: RXN_LSCREEN_060207_023.D (-)
356
800000
700000
600000
500000
400000
300000
283
200000
256
100000
43
88
0
70
160
118 142
183
212 238
328
301
384 412
440
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 495 -
HDPE76
Abundance
130000
Average of 30.373 to 30.430 min.: RXN_LSCREEN_060207_023.D (-)
389
120000
110000
100000
333
90000
80000
57
70000
60000
50000
40000
30000
282
20000
10000
183
91
427
147
117
165
201
235 259
359
315
0
407
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE77
Abundance
60000
Average of 30.621 to 30.663 min.: RXN_LSCREEN_060207_023.D (-)
382
57
55000
50000
45000
40000
35000
85
30000
25000
20000
15000
10000
256
309
111
5000
0
155
131
238
183
211
356
281
337
416
449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 496 -
HDPE78
Abundance
Average of 30.616 to 30.654 min.: RXN_LSCREEN_060207_023.D (-)
71
9500
9000
8500
8000
7500
356
7000
6500
6000
5500
5000
4500
4000
3500
97
3000
2500
2000
308
1500
250
117
1000
135
500
46
416
208
163
182
278
336
375 399
230
435
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
HDPE79
Abundance
Average of 30.854 to 30.906 min.: RXN_LSCREEN_060207_023.D (-)
256
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
43
356
283
60000
238
88
40000
70
20000
126
168
186
107
147
0
40
60
212
328
307
412
374394
440
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 497 -
HDPE80
Abundance
Average of 31.795 to 31.857 min.: RXN_LSCREEN_060207_023.D (-)
389
1100000
1000000
900000
800000
700000
600000
500000
333
400000
57
300000
200000
183
100000
91
0
40
60
117
147
165
201
427
282
235 259
315
356
407
448
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
Codes correspond to Table 20 in the main report
PS1
Abundance
Scan 415 (8.568 min): FSA_203.D (-405) (-)
57
7000
6500
6000
5500
5000
4500
4000
3500
41
3000
2500
2000
29
1500
70
83
1000
98
500
17
0
5
65
51
91
78
106 112
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
580
432
0
0
50
100
150
200
250
300
m/z-->
PS3
- 499 -
350
400
450
500
550
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
131
143
0
20
40
60
80
100
120
140
207
160
180
200
232
220
250
240
281
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
77
1500
41
1000
500
222
0
0
50
100
150
200
250
316355
300
350
774
400
m/z-->
- 500 -
450
500
550
600
650
700
750
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
0
0
50
100
150
200
250
300
350
400
699
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
0
16
28
20
44
40
60
60
76
80
107
95
119
100
120
161
173
140
m/z-->
- 501 -
160
193206220
180
200
220
281
240
260
280
PS7
Abundance
Scan 1512 (18.173 min): FSA_203.D (-1507) (-)
135
60000
55000
107
50000
149
45000
40000
35000
30000
121
25000
20000
15000
41 55
77 91
10000
0
191
29
5000
220
208
235
161175
17
20
40
60
80
282295
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
0
0
50
100
150
200
250
300
403
350
400
m/z-->
- 502 -
745784
450
500
550
600
650
700
750
PS9
Abundance
Scan 1537 (18.392 min): FSA_203.D (-1533) (-)
135
24000
22000
121
107
20000
18000
16000
14000
12000
10000
163
8000
41
6000
4000
2000
177
77 91
27
55
197
0
20
40
60
80
220
278 296 316
237
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
0
50
100
150
200
250
385 417
300
m/z-->
- 503 -
350
400
575
450
500
550
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
0
65 84
16
20
40
60
194 220
162
248
281
322341
411
80 100120140160180200220240260280300320340360380400
m/z-->
PS12
Abundance
Scan 1574 (18.716 min): FSA_203.D (-1580) (-)
135
26000
25000
24000
23000
22000
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
41
3000
91
2000
1000
178
220
0
0
50
100
150
200
265302
250
300
358
350
453
400
m/z-->
- 504 -
450
767
500
550
600
650
700
750
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
41
1500
1000
77
500
0
155
175
17
50
100
150
209
234
200
261283
250
300
447
350
400
450
m/z-->
PS14
Abundance
Scan 1676 (19.609 min): FSA_203.D (-1672) (-)
161
7000
6000
5000
4000
135
3000
235
2000
41
1000
0
91
190
15
0
50
100
150
200
281
250
300
m/z-->
- 505 -
602
350
400
450
500
550
600
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
128
400
200
190
81
281
221
489
550
0
0
50
100
150
200
250
300
350
400
450
500
550
m/z-->
PS16
Abundance
Average of 21.894 to 21.955 min.: FSA_203.D (-)
225
1200000
1100000
1000000
900000
800000
700000
600000
500000
93
400000
300000
168
200000
51
100000
0
127
15
0
50
100
150
258297
200
250
300
354
350
404 447
400
m/z-->
- 506 -
450
571 613
500
550
600
663
650
725
700
776
750
PS17
Abundance
Scan 1788 (20.589 min): FSA_218.D (-1779) (-)
135
223
35000
45
30000
25000
20000
15000
10000
107
5000
77
161
19
0
0
50
100
150
192
200
263
250
294
323
300
595
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
2000
213
61
26
0
0
20
233
40
60
276
306
329
374
80 100120140160180200220240260280300320340360380400
m/z-->
- 507 -
PS19
Abundance
Scan 2334 (25.370 min): FSA_203.D (-2326) (-)
149
60000
55000
50000
45000
40000
35000
30000
57
25000
20000
15000
10000
113
5000
29
279
210233257
189
84
0
0
50
100
150
200
250
318
339362387
300
350
426
400
505
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
0
113
279
207
15
0
245
50
100
150
200
250
333
300
350
391429 473
400
m/z-->
- 508 -
450
535
500
550
607
600
697
732 780
650
700
750
PS21
Abundance
Average of 39.930 to 40.035 min.: FSA_203.D (-)
161
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
57
20000
15000
10000
121
217
0
368
263
5000
312
19
0
50
100
150
200
250
300
350
415
400
m/z-->
- 509 -
474
450
530
500
586
619
652
685 725
550
600
650
700
785
750
Mass spectra of the peaks detected in the extracts of the PET + additive samples
that were not present in the PET samples
Codes correspond to Table 21 in the main report
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
Average of 32.873 to 32.943 min.: FSA_197.D (-)
48000
91
46000
44000
42000
40000
38000
432
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
41
12000
342
165
10000
8000
128
6000
4000
209
2000
252
284
388
0
0
50
100
150
200
250
300
350
m/z-->
- 510 -
400
475 516
450
500
563 609647 689
550
600
650
700
759
750
Mass spectra of the peaks detected in the extracts of the PVC + additive samples
that were not present in the PVC samples
Codes correspond to Table 22 in the main report
PVC1
Abundance
700000
Average of 3.856 to 3.985 min.: RXN_LSCREEN_160207_035.D (-)
47
650000
600000
550000
500000
450000
120
400000
350000
74
300000
250000
200000
150000
100000
92
50000
145
163 189
0
40
60
221
249
284305325
343
266
369
386
416
446
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC2
Abundance
Average of 4.170 to 4.203 min.: RXN_LSCREEN_160207_035.D (-)
161
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
105
8000
7000
6000
77
5000
4000
133
3000
59
2000
1000
40
209
191
0
40
60
238
268
295
313
342
385
367
415
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 511 -
PVC3
Abundance
Average of 4.284 to 4.351 min.: RXN_LSCREEN_060207_036.D (-)
43
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000
68
1000
129
147165
99
0
193
259 281
219 241
315 341 366
401
430
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC4
Abundance
Average of 4.450 to 4.465 min.: RXN_LSCREEN_060207_036.D (-)
57
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000
20000
99
40
79
0
40
60
133 155
172192
116
208 230
259 282 307327
344
401
383
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 512 -
PVC5
Abundance
Average of 4.503 to 4.531 min.: RXN_LSCREEN_060207_036.D (-)
83
30000
28000
26000
24000
22000
20000
18000
16000
43
14000
12000
129
10000
8000
6000
4000
111
2000
60
159 185203 229
0
40
60
259
276295
327
355
404
434
80 100120140160180200220240260280300320340360380400420
m/z-->
PVC6
Abundance
Average of
81
4.940 to 5.054 min.:
RXN_LSCREEN_060207_036.D (-)
52000
50000
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
138
53
8000
6000
4000
2000
109
159 181
0
40
60
207
234 257
283
301
327
355 378
418
448
80 100
120140160180
200220240
260280300
320340360380
400420440
m/z-->
- 513 -
PVC7
Abundance
Average of 5.102 to 5.188 min.: RXN_LSCREEN_060207_036.D (-)
41
18000
17000
16000
15000
14000
13000
12000
11000
84
10000
9000
8000
7000
6000
5000
4000
3000
120
2000
66
1000
152
170 193
101
0
40
60
219238 259 281300
326
356
387
429
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC8
Abundance
7000000
Average of 5.487 to 5.606 min.: RXN_LSCREEN_060207_036.D (-)
57
6500000
6000000
5500000
5000000
83
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
112
500000
0
130
165185 207 229
259281
313 341 364383402
431
449
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 514 -
PVC9
Abundance
Average of 6.196 to 6.262 min.: RXN_LSCREEN_060207_036.D (-)
57
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
83
80000
60000
40000
112
20000
134
0
40
60
161
179
207
234 259 282
309 334355
374
403
430
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC10
Abundance
Average of 6.433 to 6.476 min.: RXN_LSCREEN_060207_036.D (-)
113
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
59
6000
85
4000
2000
40
143
0
40
60
165185 208
243 267 291 316
226
342 365 389 412
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 515 -
PVC11
Abundance
Average of 6.524 to 6.548 min.: RXN_LSCREEN_060207_036.D (-)
57
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
83
15000
10000
113
5000
141
158
0
40
60
185
215
232
249
281
299 323
356
400
431
80 100120140160180200220240260280300320340360380400420
m/z-->
PVC12
Abundance
Average of 6.614 to 6.662 min.: RXN_LSCREEN_060207_036.D (-)
57
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
98
8000
6000
4000
2000
79
0
40
60
124
185 209 234
148
252
167
281
309
341362 385
414
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 516 -
PVC13
Abundance
Average of 6.572 to 6.610 min.: RXN_LSCREEN_160207_035.D (-)
207
11000
10500
10000
9500
9000
117
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
43
3500
3000
237
2500
2000
89
1500
281
179
1000
145
61
500
327
255
0
40
60
299
356
385
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC14
Abundance
Average of 6.980 to 7.018 min.: RXN_LSCREEN_060207_036.D (-)
56
16000
15000
14000
13000
12000
11000
10000
83
9000
8000
146
7000
6000
5000
4000
3000
112
2000
355
1000
129
0
40
60
185
168
207
237
267
296
327
385 408429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 517 -
PVC15
Abundance
Average of 7.180 to 7.275 min.: RXN_LSCREEN_060207_036.D (-)
1100000
43
1000000
70
900000
800000
700000
600000
500000
400000
300000
200000
112
100000
91
0
40
60
139
157
185 209
236 262281 305
323
341
369
398
417 439
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC16
Abundance
170000
Average of 7.247 to 7.275 min.: RXN_LSCREEN_160207_035.D (-)
43
160000
150000
140000
130000
120000
110000
100000
90000
80000
120
70000
60000
50000
40000
30000
89
162
20000
10000
61
141
0
40
60
194
222
267
249
295
313
341
371
401
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 518 -
PVC17
Abundance
Average of 7.518 to 7.575 min.: RXN_LSCREEN_060207_036.D (-)
99
7500000
7000000
6500000
6000000
5500000
5000000
127
4500000
4000000
3500000
3000000
2500000
2000000
54
1500000
1000000
500000
72
145
172
0
207 229
259281 305325
343 369
401
430
448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC18
Abundance
Average of 7.641 to 7.670 min.: RXN_LSCREEN_060207_036.D (-)
57
32000
30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000
118
2000
89
0
40
60
147
167
185
207
232
259 283 309329
356
385405 429
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 519 -
PVC19
Abundance
Average of 7.779 to 7.832 min.: RXN_LSCREEN_060207_036.D (-)
127
280000
260000
240000
220000
200000
180000
99
160000
140000
120000
100000
80000
60000
55
40000
81
20000
145
0
40
60
173193 219240259 281
309 333
351
369
401
431
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC20
Abundance
Average of 7.865 to 7.908 min.: RXN_LSCREEN_060207_036.D (-)
41
6000
5500
69
5000
4500
4000
3500
3000
97
2500
2000
1500
168
1000
140
119
500
187207
235
0
40
60
267
284304 327
357
382
415
432
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 520 -
PVC21
Abundance
Average of 7.665 to 7.684 min.: RXN_LSCREEN_160207_035.D (-)
267
6500
6000
5500
5000
4500
4000
3500
341
3000
2500
285
2000
1500
311
1000
56
193
82
112
500
237
141
163
0
401
211
369
429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC22
Abundance
Average of 7.722 to 7.741 min.: RXN_LSCREEN_160207_035.D (-)
88
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
57
14000
127
12000
10000
8000
6000
4000
2000
109
0
40
60
151172
207
237
282
265
304325
356
401
383
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 521 -
PVC23
Abundance
Average of 7.984 to 8.027 min.: RXN_LSCREEN_060207_036.D (-)
57
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
85
14000
12000
10000
8000
113
6000
4000
170
2000
141
193
229
211
0
40
60
259 283
300
327
355
387406 427447
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC24
Abundance
8500
Average of 8.107 to 8.131 min.: RXN_LSCREEN_060207_036.D (-)
43
8000
7500
7000
6500
6000
5500
5000
70
4500
4000
3500
3000
112
2500
2000
95
1500
1000
500
138
156
187208 233
0
40
60
259 281
307327 348369 395
431
80 100120140160180200220240260280300320340360380400420
m/z-->
- 522 -
PVC25
Abundance
Average of 8.117 to 8.131 min.: RXN_LSCREEN_160207_035.D (-)
217
4500
105
4000
133
3500
3000
2500
2000
45
75
1500
1000
265
500
161
195
284
0
40
60
402
325
235
306
344
430
373
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC26
Abundance
Average of 8.150 to 8.179 min.: RXN_LSCREEN_160207_035.D (-)
133
6000
5500
5000
4500
4000
3500
3000
59
103
163
2500
2000
250
41
1500
269
208
1000
77
357
500
181
230
0
40
60
311
293
402
339
383
429
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 523 -
PVC27
Abundance
Average of 8.493 to 8.516 min.: RXN_LSCREEN_060207_036.D (-)
57
5000
125
4500
4000
3500
3000
2500
2000
84
1500
1000
415
327
185 207
500
105
40
166
148
235
0
40
60
267
284 307
355
383
80 100120140160180200220240260280300320340360380400420
m/z-->
PVC28
Abundance
Average of 8.502 to 8.550 min.: RXN_LSCREEN_160207_035.D (-)
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
281
207
237
500
156
255
0
40
60
311
359
403
429
446
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 524 -
PVC29
Abundance
Average of 8.768 to 8.811 min.: RXN_LSCREEN_060207_036.D (-)
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
0
40
60
191
209
235 259 283
309
341
380
397415
432
80 100120140160180200220240260280300320340360380400420
m/z-->
PVC30
Abundance
Average of 8.916 to 8.978 min.: RXN_LSCREEN_060207_036.D (-)
117
17000
16000
71
15000
14000
13000
12000
11000
89
10000
9000
8000
7000
6000
5000
53
4000
3000
2000
145
1000
174
208
191
0
40
60
235
267
297
315
341359
386
402
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 525 -
PVC31
Abundance
Average of 9.006 to 9.021 min.: RXN_LSCREEN_060207_036.D (-)
85
18000
17000
16000
15000
14000
43
13000
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
104
62
0
40
60
191
135155
209
173
235
268
331
313
295
362382401
430
80 100120140160180200220240260280300320340360380400420
m/z-->
PVC32
Abundance
Average of 9.054 to 9.078 min.: RXN_LSCREEN_060207_036.D (-)
57
65000
60000
55000
50000
45000
40000
101
75
35000
41
30000
25000
20000
15000
10000
124
150
186
5000
169
0
40
60
209
238 262280
313
341
376395414
80 100120140160180200220240260280300320340360380400
m/z-->
- 526 -
PVC33
Abundance
Average of 8.902 to 8.949 min.: RXN_LSCREEN_160207_035.D (-)
281
10500
10000
9500
9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
103
3500
3000
2500
355
73
2000
191
43
1500
251
149
1000
325
221
131
500
172
301
0
40
60
385
403
431
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC34
Abundance
Average of 9.296 to 9.315 min.: RXN_LSCREEN_060207_036.D (-)
43
20000
19000
69
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
87
7000
129
6000
5000
4000
3000
2000
105
1000
159
193
221
0
40
60
251
282301321341
358 382
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 527 -
PVC35
Abundance
Average of 9.401 to 9.430 min.: RXN_LSCREEN_060207_036.D (-)
57
48000
46000
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
85
18000
16000
14000
12000
10000
8000
6000
184
4000
112
2000
141
165
0
40
60
207
236 259 281301
327
357
401
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC36
Abundance
Average of 9.472 to 9.506 min.: RXN_LSCREEN_060207_036.D (-)
70
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
8000
41
7000
6000
5000
4000
91 112
3000
149
2000
130
1000
235 259 281
167 191 217
0
40
60
327
309
429
355
373393
411
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 528 -
PVC37
Abundance
Average of 9.620 to 9.648 min.: RXN_LSCREEN_060207_036.D (-)
57
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
83
80000
60000
112
40000
20000
157
139
0
40
60
185 209 230
259 281 306
324
341
370
402 425
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC38
Abundance
Average of 9.667 to 9.701 min.: RXN_LSCREEN_060207_036.D (-)
89
5000
4500
4000
3500
3000
2500
147
2000
40
114
1500
1000
500
60
207
167 189
228 249
0
40
60
281
341
303
377 401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
- 529 -
PVC39
Abundance
Average of 9.753 to 9.772 min.: RXN_LSCREEN_060207_036.D (-)
145
170000
160000
150000
140000
103
130000
120000
110000
100000
90000
71
80000
70000
60000
50000
40000
30000
45
174
128
20000
10000
87
0
40
60
80
190207
237
267
283
311329
356 378
415
100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400
m/z-->
PVC40
Abundance
Average of 9.734 to 9.805 min.: RXN_LSCREEN_160207_035.D (-)
120
8000
7500
7000
6500
6000
5500
43
5000
73
4500
190
4000
3500
3000
101
2500
2000
144
1500
415
1000
500
162
210
237
281
255
0
40
60
356
328
308
387
439
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 530 -
PVC41
Abundance
100000
Average of 10.105 to 10.129 min.:
99
RXN_LSCREEN_060207_036.D (-)
95000
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
127
30000
25000
20000
15000
47
10000
145
82
5000
162
64
0
40
60
209 233
190
259 281 303 325
342 364
395416
80 100120140160180200220240260280300320340360380400420
m/z-->
PVC42
Abundance
Average of 10.152 to 10.167 min.: RXN_LSCREEN_060207_036.D (-)
57
400000
380000
360000
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
83
140000
120000
100000
80000
60000
112
40000
20000
157177
139
0
40
60
208
234 259 281
309329348
377 401421
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 531 -
PVC43
Abundance
Average of 9.986 to 10.005 min.: RXN_LSCREEN_160207_035.D (-)
133
65000
60000
55000
203
50000
45000
40000
35000
156
30000
177
25000
75
20000
15000
10000
109
248
45
5000
230
281
299
0
40
60
328
355
387
417
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC44
Abundance
18000
Average of 10.290 to 10.338 min.: RXN_LSCREEN_160207_035.D (-)
127
17000
16000
145
15000
14000
13000
12000
11000
10000
56
99
9000
8000
7000
6000
5000
4000
3000
245
81
2000
1000
175
0
40
60
210
282
264
311
329
415
355
385
433
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 532 -
PVC45
Abundance
36000
Average of 10.599 to 10.614 min.: RXN_LSCREEN_060207_036.D (-)
43
34000
32000
30000
28000
26000
24000
115
22000
20000
18000
16000
14000
143
12000
71
10000
8000
6000
89
4000
2000
163
0
40
60
196
233
215
267
285 309
340
379
415
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC46
Abundance
Average of 10.652 to 10.661 min.: RXN_LSCREEN_060207_036.D (-)
41
20000
19000
18000
17000
16000
83
15000
14000
13000
12000
11000
10000
9000
8000
7000
6000
111
5000
4000
3000
2000
143
1000
64
168
196
215
0
40
60
249
267286
321341360 381
415
80 100120140160180200220240260280300320340360380400420
m/z-->
- 533 -
PVC47
Abundance
Average of 10.647 to 10.680 min.: RXN_LSCREEN_160207_035.D (-)
113
220000
200000
180000
160000
140000
120000
86
141
100000
80000
60000
41
40000
68
159
20000
193214233253
0
283 309
341
387
369
417
446
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC48
Abundance
36000
Average of 10.695 to 10.718 min.: RXN_LSCREEN_160207_035.D (-)
160
34000
32000
30000
28000
26000
24000
22000
105
77
20000
133
18000
16000
14000
206
45
12000
10000
8000
6000
4000
267
2000
178
0
40
60
238
341
299 323
387
369
405 429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 534 -
PVC49
Abundance
Average of 10.795 to 10.842 min.: RXN_LSCREEN_160207_035.D (-)
43
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
120
18000
71
16000
14000
12000
10000
144
8000
190
6000
4000
102
2000
163
0
40
60
208 233
251
281
313
342
371
401
430
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC50
Abundance
Average of 10.961 to 11.009 min.: RXN_LSCREEN_160207_035.D (-)
191
21000
20000
19000
18000
17000
16000
15000
14000
13000
12000
11000
10000
9000
105
8000
7000
57
6000
5000
4000
3000
87
131
163
2000
1000
237
217
0
40
60
268
295
341
323
387
369
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 535 -
PVC51
Abundance
Average of 11.180 to 11.227 min.: RXN_LSCREEN_060207_036.D (-)
71
5000000
43
4500000
4000000
3500000
3000000
112
2500000
2000000
1500000
92
1000000
145
500000
175
0
40
60
204 229
247267
285 311
341362381401
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC52
Abundance
Average of 12.145 to 12.292 min.: RXN_LSCREEN_060207_036.D (-)
205
8000000
7500000
7000000
6500000
6000000
5500000
5000000
4500000
4000000
57
145
3500000
3000000
177
2500000
105
2000000
1500000
81
1000000
500000
0
127
223
241
259281 307
341360 387
415 437
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 536 -
PVC53
Abundance
Average of 12.102 to 12.126 min.: RXN_LSCREEN_160207_035.D (-)
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
131
1000
177
223
40
60
281
327
307
0
416
352
383
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC54
Abundance
Average of 12.178 to 12.216 min.: RXN_LSCREEN_160207_035.D (-)
60
5000
4500
4000
3500
3000
41
251
207
2500
2000
341
99
1500
137
1000
79
177
117
500
389
159
225
0
40
60
309
269
289
365
418
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 537 -
PVC55
Abundance
Average of 12.592 to 12.635 min.: RXN_LSCREEN_060207_036.D (-)
57
600000
550000
500000
450000
400000
350000
300000
85
250000
200000
112
150000
140
100000
50000
168
0
40
60
211
194
234
251
281
327
310
354
382401
429
80 100120140160180200220240260280300320340360380400420
m/z-->
PVC56
Abundance
Average of 12.763 to 12.844 min.: RXN_LSCREEN_060207_036.D (-)
57
190000
101
180000
170000
160000
129
150000
140000
130000
120000
83
110000
100000
90000
80000
199
70000
60000
50000
157
40000
30000
224
20000
10000
175
252
0
40
60
281
327
309
355
388
415
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 538 -
PVC57
Abundance
Average of 13.053 to 13.110 min.: RXN_LSCREEN_060207_036.D (-)
83
36000
112
34000
32000
30000
28000
26000
24000
22000
20000
224
18000
16000
14000
12000
190
10000
8000
6000
65
4000
2000
135
47
162
249268289309
0
40
60
341360 382
415435
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC58
Abundance
Average of 12.716 to 12.740 min.: RXN_LSCREEN_160207_035.D (-)
119
30000
28000
26000
24000
43
22000
20000
18000
16000
14000
190
91
12000
10000
8000
6000
65
4000
2000
159
138
0
40
224
254275295
327
355
388
405 429
447
60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 539 -
PVC59
Abundance
32000
Average of 12.778 to 12.825 min.: RXN_LSCREEN_160207_035.D (-)
43
30000
28000
155
26000
117
24000
22000
20000
18000
16000
99
14000
12000
173
10000
8000
73
6000
207
4000
341
2000
225
137
0
254 281
309
387
369
417 443
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC60
Abundance
5500000
Average of 12.901 to 12.916 min.: RXN_LSCREEN_160207_035.D (-)
113
5000000
4500000
4000000
3500000
3000000
2500000
2000000
57
86
1500000
1000000
131
169
500000
187
150
0
40
60
213
242262
281
309
327
355
387
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 540 -
PVC61
Abundance
240000
Average of 12.949 to 12.992 min.: RXN_LSCREEN_160207_035.D (-)
43
71
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000
99
226
20000
127
154
183 207
0
251
281
313
341
387
369
447
405 429
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC62
Abundance
7000000
Average of 13.229 to 13.286 min.: RXN_LSCREEN_060207_036.D (-)
57
6500000
6000000
5500000
5000000
4500000
4000000
85
3500000
3000000
2500000
113
2000000
1500000
1000000
500000
0
141
226
169
197
259 281
309
341 363 385
415 439
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 541 -
PVC63
Abundance
55000
Average of 13.225 to 13.248 min.: RXN_LSCREEN_160207_035.D (-)
217
50000
45000
40000
35000
30000
25000
20000
15000
10000
57
112
5000
91
157
139
189
235
253 275
293
0
323
355
385404 430
448
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC64
Abundance
75000
Average of 13.258 to 13.277 min.: RXN_LSCREEN_160207_035.D (-)
112
70000
65000
60000
55000
50000
139
45000
212
40000
35000
30000
84
167
25000
20000
185
15000
10000
43
5000
66
239258
0
40
60
285 309
342 367
385
402
430449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 542 -
PVC65
Abundance
36000
Average of 13.344 to 13.363 min.: RXN_LSCREEN_160207_035.D (-)
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
137
215
0
40
60
282
263
328
310
356
388
416
444
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC66
Abundance
Average of 13.558 to 13.586 min.: RXN_LSCREEN_160207_035.D (-)
112
260000
240000
220000
200000
180000
160000
140000
120000
169
100000
80000
57
60000
131
85
40000
187
20000
149
0
40
60
242261281
205224
309328
355
401
383
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 543 -
PVC67
Abundance
Average of 13.648 to 13.662 min.: RXN_LSCREEN_160207_035.D (-)
157
90000
85000
80000
75000
70000
65000
60000
55000
50000
45000
40000
35000
115
30000
25000
20000
203
43
15000
10000
301
69 87
5000
139
185
0
40
60
238
265
284
325
355
373
433
392 415
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC68
Abundance
8000000
Average of 13.957 to 14.028 min.: RXN_LSCREEN_060207_036.D (-)
71
7500000
7000000
6500000
6000000
43
5500000
5000000
4500000
4000000
3500000
3000000
112
2500000
2000000
1500000
1000000
500000
0
131
89
157
185
203222242 267
285 309
341360381401
419
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 544 -
PVC69
Abundance
Average of 13.748 to 13.757 min.: RXN_LSCREEN_160207_035.D (-)
45
6000
5500
5000
4500
4000
3500
163
205
3000
334
89
2500
133
2000
1500
267
415
1000
355
500
249
65
186
225
388
445
295
315
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC70
Abundance
Average of 14.190 to 14.318 min.: RXN_LSCREEN_060207_036.D (-)
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
0
40
60
249
283 309329351
383
415
444
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 545 -
PVC71
Abundance
Average of 14.028 to 14.071 min.: RXN_LSCREEN_160207_035.D (-)
43
18000
17000
126
16000
15000
81
14000
13000
12000
11000
10000
9000
8000
154
7000
6000
5000
210
4000
3000
238
2000
387
191
341
108
61
1000
311
269 293
0
40
60
415
445
367
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC72
Abundance
300000
Average of 14.147 to 14.290 min.: RXN_LSCREEN_160207_035.D (-)
43
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
60000
40000
20000
126
73
0
40
60
105
154
183 207
341
256 281301 323
238
367387
418
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 546 -
PVC73
Abundance
Average of 14.585 to 14.632 min.: RXN_LSCREEN_060207_036.D (-)
155
173
38000
36000
34000
32000
30000
56
28000
26000
91
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000
225
135
2000
196
113
0
40
60
251
281
328
310
355
385
416436
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC74
Abundance
Average of 14.656 to 14.703 min.: RXN_LSCREEN_060207_036.D (-)
105
36000
34000
32000
30000
28000
26000
24000
22000
20000
70
18000
16000
14000
12000
10000
8000
123
6000
4000
2000
0
49
40
60
88
142
163 184
202
225
267
242
284 309
341
358 381401 422 445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 547 -
PVC75
Abundance
Average of 14.822 to 14.860 min.: RXN_LSCREEN_060207_036.D (-)
91
900000
173
800000
700000
155
600000
500000
56
400000
300000
200000
100000
203
74
0
115
133
228 250 273293
329 355
311
384
401
430
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC76
Abundance
Average of 14.922 to 14.975 min.: RXN_LSCREEN_060207_036.D (-)
91
750000
173
700000
650000
600000
155
550000
500000
450000
400000
56
350000
300000
250000
200000
150000
100000
50000
109
0
40
60
134
203
228
246
273
307327
355
381401
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 548 -
PVC77
Abundance
40000
Average of 14.746 to 14.808 min.: RXN_LSCREEN_160207_035.D (-)
103
38000
36000
34000
32000
30000
28000
26000
43
24000
22000
20000
18000
16000
159
229
211
14000
12000
140
75
10000
8000
260
183
6000
4000
2000
343
281
122
0
40
60
313
387
369
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC78
Abundance
Average of 15.084 to 15.127 min.: RXN_LSCREEN_060207_036.D (-)
43
700000
145
650000
600000
550000
500000
450000
400000
89
350000
300000
250000
200000
150000
71
100000
215
117
50000
187
246
166
0
40
60
268 289309
342
361 382
415
433
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 549 -
PVC79
Abundance
Average of 15.141 to 15.160 min.: RXN_LSCREEN_160207_035.D (-)
88
75000
70000
65000
60000
149
55000
207
50000
57
45000
40000
35000
30000
131
25000
279
20000
249
15000
10000
225
408
5000
112
167
185
298
0
40
60
326
356
385
445
427
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC80
Abundance
Average of 15.236 to 15.241 min.: RXN_LSCREEN_160207_035.D (-)
112
700000
650000
600000
550000
500000
139
450000
185
400000
350000
300000
250000
200000
212
84
150000
157
41
241
100000
50000
66
266286307327
0
40
60
355
388
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 550 -
PVC81
Abundance
Average of 15.298 to 15.327 min.: RXN_LSCREEN_160207_035.D (-)
112
300000
280000
260000
240000
220000
185
139
200000
180000
160000
140000
120000
100000
212
84
80000
157
41
60000
241
40000
20000
66
286
268
0
40
60
313
343 369
399
429
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC82
Abundance
Average of
15.417 to 15.445 min.:
172
128
RXN_LSCREEN_160207_035.D (-)
800000
750000
700000
650000
600000
550000
500000
73
450000
400000
219
246
350000
100
300000
55
250000
200000
292
150000
100000
147
200
50000
267
0
40
60
355
313 337
381402
430
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 551 -
PVC83
Abundance
Average of 16.468 to 16.553 min.: RXN_LSCREEN_060207_036.D (-)
57
75000
70000
65000
60000
55000
50000
45000
85
40000
35000
30000
25000
20000
15000
127
10000
268
155
5000
182
107
211
239
0
40
60
307327
289
355
374394415
446
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC84
Abundance
Average of 16.254 to 16.287 min.: RXN_LSCREEN_160207_035.D (-)
157
4000000
3500000
3000000
2500000
203
2000000
1500000
43
1000000
115
500000
185
139
245
67
0
85
227
273
301
327
355
388
415
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 552 -
PVC85
Abundance
Average of 16.853 to 16.901 min.: RXN_LSCREEN_060207_036.D (-)
57
75000
70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
160
15000
132
10000
83
190
103
5000
274
217
253
235
0
40
60
311
292
343 365
383
416
433
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC86
Abundance
Average of 16.254 to 16.287 min.: RXN_LSCREEN_160207_035.D (-)
157
4000000
3500000
3000000
2500000
203
2000000
1500000
43
1000000
115
500000
185
139
245
67
0
85
227
273
301
327
355
388
415
445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 553 -
PVC87
Abundance
Average of 17.386 to 17.428 min.: RXN_LSCREEN_060207_036.D (-)
88
450000
400000
350000
300000
250000
200000
43
150000
100000
157
70
284
241
50000
115
185
213
139
259
0
40
60
311
341
358 385
403 429
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC88
Abundance
Average of 18.156 to 18.294 min.: RXN_LSCREEN_060207_036.D (-)
157
750000
700000
650000
185
600000
231
550000
500000
450000
400000
43
350000
300000
250000
129
200000
150000
100000
111
50000
87
69
301
273
213
329
249
0
40
60
355
373
401
429
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 554 -
PVC89
Abundance
Average of 18.922 to 19.640 min.: RXN_LSCREEN_060207_036.D (-)
112
2400000
156
2200000
2000000
1800000
1600000
1400000
138
1200000
1000000
800000
600000
400000
42
212
71
200000
94
239
257 281
184
0
40
60
310
328
355
383
401
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC90
Abundance
8000000
Average of 19.820 to 20.762 min.: RXN_LSCREEN_060207_036.D (-)
41
129
259
185
7500000
7000000
6500000
157
6000000
5500000
5000000
4500000
4000000
111
3500000
329
213
3000000
2500000
2000000
84
1500000
1000000
500000
61
241
403
301
281
0
361
383
429
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 555 -
PVC91
Abundance
Average of 20.225 to 20.249 min.: RXN_LSCREEN_160207_035.D (-)
145
200000
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
55
20000
269
10000
219
335
0
40
60
384
413
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC92
Abundance
9000
Average of 20.272 to 20.291 min.: RXN_LSCREEN_160207_035.D (-)
343
8500
8000
7500
7000
6500
6000
5500
5000
4500
315
4000
3500
3000
2500
2000
40
221
1500
169
94
240
500
62
122
60
389
371
0
40
431
287
266
192
1000
413
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 556 -
PVC93
Abundance
Average of 20.310 to 20.334 min.: RXN_LSCREEN_160207_035.D (-)
166
6000
5500
138
5000
4500
199
4000
3500
40
3000
2500
295
95
221
240
2000
271
1500
1000
369
323
62
118
500
347
432
400
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC94
Abundance
60000
Average of 20.439 to 20.453 min.: RXN_LSCREEN_160207_035.D (-)
112
157
55000
50000
45000
40000
241
55
139
35000
30000
25000
185
20000
315
15000
10000
213
84
269
5000
297
0
341
371 396416
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 557 -
PVC95
Abundance
Average of 20.491 to 20.505 min.: RXN_LSCREEN_160207_035.D (-)
55
85000
80000
75000
70000
81
65000
60000
55000
50000
45000
40000
35000
30000
99
25000
121
20000
164
15000
10000
139
279
207
247
5000
189
0
40
60
303
322341361 386
229
416
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC96
Abundance
Average of 20.510 to 20.558 min.: RXN_LSCREEN_160207_035.D (-)
112
44000
42000
40000
38000
36000
34000
32000
30000
28000
26000
24000
22000
20000
18000
16000
259
14000
12000
303
212
10000
174
8000
87
6000
152
4000
231
63
277
329
2000
134
40
0
40
60
361
406
386
448
430
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 558 -
PVC97
Abundance
Average of 20.620 to 20.696 min.: RXN_LSCREEN_160207_035.D (-)
155
55
4500000
4000000
88
3500000
3000000
2500000
2000000
109
1500000
1000000
185
213
136
500000
281
263
245
0
40
60
326
308
355
387
415
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC98
Abundance
Average of 20.800 to 20.819 min.: RXN_LSCREEN_160207_035.D (-)
56
280000
260000
285
240000
220000
200000
180000
160000
140000
120000
267
100000
129
80000
60000
185
40000
87
241
20000
108
0
40
60
150
167
222
204
313
331 357
388 413432
450
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 559 -
PVC99
Abundance
Average of 21.123 to 21.142 min.: RXN_LSCREEN_060207_036.D (-)
57
340000
320000
300000
280000
260000
240000
220000
200000
99
180000
160000
169
140000
120000
241
100000
80000
60000
151
297
40000
126
20000
197
81
223
0
40
60
261
279
315
353
371
335
401
431
450
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC100
Abundance
Average of 21.152 to 21.171 min.: RXN_LSCREEN_060207_036.D (-)
155
500000
55
450000
400000
88
350000
300000
250000
200000
109
150000
206
100000
136
50000
188
237
0
40
262
281
318
346
374
406426 449
60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 560 -
PVC101
Abundance
Average of 20.848 to 20.872 min.: RXN_LSCREEN_160207_035.D (-)
88
900000
800000
700000
600000
500000
400000
340
300000
157
200000
297
100000
61
115
135
185
213
241
269
0
322
360 383
401
419
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC102
Abundance
2800000
Average of 21.071 to 21.100 min.: RXN_LSCREEN_160207_035.D (-)
258
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
215
1000000
800000
75
600000
400000
55
200000
101
129
287
337
163
187
239
0
40
60
313
355
385
415
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 561 -
PVC103
Abundance
Average of 21.390 to 21.404 min.: RXN_LSCREEN_060207_036.D (-)
273
210000
200000
190000
180000
170000
160000
150000
185
140000
293
129
130000
120000
110000
100000
90000
80000
70000
60000
219
50000
89
40000
30000
147
20000
343
374
61
10000
315
237
429
393
411
447
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC104
Abundance
Average of 21.119 to 21.133 min.: RXN_LSCREEN_160207_035.D (-)
286
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
50000
40000
30000
20000
315
257
74
10000
40
94
0
40
60
120
146
198
180
237
340 363
396417
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 562 -
PVC105
Abundance
Average of 21.437 to 21.452 min.: RXN_LSCREEN_060207_036.D (-)
185
650000
600000
259
550000
500000
450000
400000
129
350000
300000
250000
43
200000
150000
157
100000
219
50000
91
363
111
307
63
237
0
40
60
277
339
394
412 437
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC106
Abundance
Average of 21.152 to 21.166 min.: RXN_LSCREEN_160207_035.D (-)
157
100000
95000
112
90000
85000
80000
75000
70000
65000
60000
57
55000
50000
139
45000
269
40000
35000
30000
25000
20000
15000
10000
212
84
5000
190
0
40
60
237
313
385
294
368
332
350
418
447
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 563 -
PVC107
Abundance
Average of 21.480 to 21.499 min.: RXN_LSCREEN_060207_036.D (-)
150
1300000
1200000
1100000
1000000
57
900000
132
800000
700000
600000
500000
400000
300000
200000
105
374
100000
287
83
262
213
244
181
0
40
60
317338
392
410431
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC108
Abundance
1000000
Average of 21.518 to 21.532 min.: RXN_LSCREEN_060207_036.D (-)
185
900000
293
800000
219
700000
600000
129
500000
400000
300000
200000
157
100000
111
55
91
0
247
73
273
329
311
363
394 421 445
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 564 -
PVC109
Abundance
140000
Average of 21.347 to 21.366 min.: RXN_LSCREEN_160207_035.D (-)
57
130000
120000
110000
100000
90000
80000
85
70000
60000
50000
40000
309
30000
20000
113
141
10000
169
337
197
225
253
281
358 383
0
40
60
416
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC110
Abundance
Average of 21.689 to 21.708 min.: RXN_LSCREEN_060207_036.D (-)
131
1500000
1400000
1300000
1200000
1100000
408
1000000
900000
800000
219
700000
600000
500000
400000
101
57
337
300000
161
189
200000
75
263
245
100000
281
0
40
60
309
366
384
426 449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 565 -
PVC111
Abundance
Average of 21.409 to 21.438 min.: RXN_LSCREEN_160207_035.D (-)
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
137
255
205
295
277
0
40
60
387
416
443
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC112
Abundance
17000
Average of 21.461 to 21.485 min.: RXN_LSCREEN_160207_035.D (-)
155
16000
15000
14000
13000
12000
11000
10000
9000
8000
7000
109
6000
5000
129
67
4000
3000
203
2000
88
1000
45
180
222242
0
40
60
265
315 341
294
369
403
431
449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 566 -
PVC113
Abundance
Average of 21.789 to 21.823 min.: RXN_LSCREEN_060207_036.D (-)
130
1100000
1000000
900000
800000
700000
600000
500000
400000
371
300000
239
101
200000
55
100000
315
75
190
149 172
0
40
60
218
257
287
343
389410
429448
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
500000
201
229
183
295
259
277
0
40
327
355
387
415434
60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 567 -
PVC115
Abundance
Average of 22.151 to 22.179 min.: RXN_LSCREEN_060207_036.D (-)
185
800000
700000
315
600000
129
57
500000
203
400000
300000
273
157
200000
100000
102
84
241
347
297
222
0
369
399
417 443
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC116
Abundance
Average of 22.212 to 22.241 min.: RXN_LSCREEN_060207_036.D (-)
149
1600000
1500000
1400000
1300000
1200000
1100000
1000000
900000
800000
700000
600000
167
500000
400000
300000
279
70
200000
100000
104
41
122
194
0
40
60
239 261
221
314
333 356 380
297
410
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 568 -
PVC117
Abundance
2600000
Average of 22.945 to 22.969 min.: RXN_LSCREEN_060207_036.D (-)
57
2400000
2200000
2000000
1800000
1600000
164
1400000
182
1200000
1000000
276
406
800000
600000
113 137
400000
294
83
200000
204
0
40
60
250
232
315
334354 380
431
450
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC118
Abundance
Average of 23.030 to 23.045 min.: RXN_LSCREEN_060207_036.D (-)
131
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
80000
101
60000
55
40000
75
203
412
265
20000
151
0
40
60
173
221 246
287
316 341
369
387
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 569 -
PVC119
Abundance
340000
Average of 22.788 to 22.817 min.: RXN_LSCREEN_160207_035.D (-)
129
320000
300000
280000
260000
229
240000
220000
200000
55
83
180000
160000
140000
155
120000
100000
80000
109
60000
40000
193
337
211
20000
263
175
60
358
319
0
40
295
387
405 429
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC120
Abundance
120000
Average of 22.893 to 22.912 min.: RXN_LSCREEN_160207_035.D (-)
159
110000
100000
90000
80000
70000
60000
50000
239
40000
30000
98 117
20000
351
177
10000
40
0
74
135
198218
311
269
293
333
383
401
419 443
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 570 -
PVC121
Abundance
130000
Average of 23.349 to 23.373 min.: RXN_LSCREEN_160207_035.D (-)
149
120000
110000
100000
90000
80000
70000
60000
50000
167
40000
293
57
83
30000
127
20000
10000
207
104
185
0
40
60
312331350
230
248267
378 400419 446
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC122
Abundance
Average of 23.516 to 23.535 min.: RXN_LSCREEN_160207_035.D (-)
71
180000
149
170000
160000
43
150000
140000
130000
120000
110000
100000
90000
80000
70000
351
60000
50000
293
127
40000
97
30000
167
20000
10000
207
225
189
0
40
60
322
253 275
379
415
397
445
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 571 -
PVC123
Abundance
Average of 23.730 to 23.758 min.: RXN_LSCREEN_160207_035.D (-)
149
300000
280000
260000
240000
220000
200000
180000
160000
140000
120000
100000
293
80000
57
60000
127
85
40000
167
20000
104
185
0
40
60
207
228248
275
312333355 378 401
429449
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC124
Abundance
550000
Average of 23.944 to 23.967 min.: RXN_LSCREEN_160207_035.D (-)
149
500000
450000
400000
350000
300000
250000
200000
293
150000
100000
43
71
127
50000
167
104
0
40
60
185 207 230250
275
320342361 387
418
436
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 572 -
PVC125
Abundance
220000
Average of 24.172 to 24.196 min.: RXN_LSCREEN_060207_036.D (-)
149
200000
180000
160000
140000
120000
100000
80000
60000
293
40000
249
121
20000
0
93
52
187
170
205 231
275
325 352
389 414 440
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC126
Abundance
Average of 23.986 to 24.025 min.: RXN_LSCREEN_160207_035.D (-)
149
220000
200000
180000
160000
140000
120000
100000
293
80000
60000
40000
43
71
127
20000
104
0
167
193213234
252 275
311 333
367386 413
447
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 573 -
PVC127
Abundance
36000
Average of 24.044 to 24.082 min.: RXN_LSCREEN_160207_035.D (-)
83
34000
32000
30000
28000
26000
24000
271
327
22000
20000
225
18000
253
55
16000
14000
12000
110
10000
148
8000
392
6000
4000
181
207
364
309
290
2000
345
427446
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC128
Abundance
Average of 24.115 to 24.148 min.: RXN_LSCREEN_160207_035.D (-)
149
400000
380000
360000
340000
320000
300000
280000
260000
240000
220000
200000
180000
160000
140000
57
120000
100000
293
80000
85
60000
127
40000
20000
104
0
40
60
167 190
208229
247
337
275
312
379
361
410
429
448
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 574 -
PVC129
Abundance
Average of 24.172 to 24.200 min.: RXN_LSCREEN_160207_035.D (-)
293
10000
9500
9000
8500
207
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
73
275
2000
127147
1500
179
1000
337
500
52
251
104
420
361
231
384
449
312
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC130
Abundance
Average of 24.315 to 24.353 min.: RXN_LSCREEN_160207_035.D (-)
57
280000
260000
240000
220000
200000
149
180000
160000
140000
85
120000
379
100000
80000
60000
40000
293
127
20000
109
0
40
60
169
197
351
275
219239
258
323
419 445
401
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 575 -
PVC131
Abundance
Average of 25.617 to 25.632 min.: RXN_LSCREEN_060207_036.D (-)
57
155
170000
160000
150000
140000
130000
120000
110000
100000
90000
80000
70000
60000
113
50000
81
40000
30000
20000
137
10000
194
173
219
247
277
295
0
40
60
323343363
393
420
440
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC132
Abundance
110000
Average of 25.432 to 25.475 min.: RXN_LSCREEN_160207_035.D (-)
57
100000
90000
80000
70000
60000
83
50000
207
40000
30000
20000
112
281
159
10000
133
188
233 255
341
307
365
392
420
441
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 576 -
PVC133
Abundance
Average of 26.060 to 26.074 min.: RXN_LSCREEN_160207_035.D (-)
57
75000
70000
65000
60000
55000
83
50000
45000
40000
35000
207
30000
25000
20000
281
112
147
15000
10000
434
351
5000
169
189
0
40
60
229
251
327
308
401
378
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC134
Abundance
Average of 26.626 to 26.669 min.: RXN_LSCREEN_160207_035.D (-)
57
100000
95000
90000
85000
80000
75000
70000
65000
60000
295
55000
207
341
50000
313
45000
40000
267
35000
149
30000
406
434
177
249
25000
20000
369
15000
123
85
10000
105
5000
225
387
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 577 -
PVC135
Abundance
Average of 26.678 to 26.688 min.: RXN_LSCREEN_160207_035.D (-)
57
110000
100000
90000
80000
295
70000
341
60000
313
207
50000
397
267
40000
30000
149
85
20000
177
249
369
434
126
10000
415
105
231
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC136
Abundance
120000
Average of 26.711 to 26.759 min.: RXN_LSCREEN_160207_035.D (-)
57
110000
100000
90000
80000
295
70000
60000
313
50000
434
40000
341
149
30000
83
20000
123
10000
267
221 249
177
406
369
195
105
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 578 -
PVC137
Abundance
Average of 26.868 to 26.887 min.: RXN_LSCREEN_160207_035.D (-)
73
207
20000
19000
18000
97
17000
281
16000
15000
14000
147
13000
12000
11000
10000
9000
8000
7000
6000
355
5000
243
4000
299
3000
2000
401
128
52
187
441
225
329
1000
383
420
261
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC138
Abundance
26000
Average of 26.940 to 26.968 min.: RXN_LSCREEN_160207_035.D (-)
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
4000
334
408
3000
277
127 149
167
2000
230
79
1000
185
211
390
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
- 579 -
PVC139
Abundance
Average of 27.406 to 27.439 min.: RXN_LSCREEN_160207_035.D (-)
57
600000
550000
313
295
500000
450000
400000
434
267
350000
300000
250000
200000
149
150000
177
207
249
369
407
334
100000
123
50000
79
105
387
231
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC140
Abundance
2000000
Average of 27.496 to 27.539 min.: RXN_LSCREEN_160207_035.D (-)
57
313
1800000
1600000
1400000
295
1200000
434
1000000
369
800000
267
334
149
600000
221
239
177
400000
408
195
123
200000
79
105
387
0
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 580 -
PVC141
Abundance
850000
Average of
27.582 to 27.629 min.:
RXN_LSCREEN_160207_035.D (-)
313
800000
750000
700000
57
650000
600000
295
550000
500000
450000
400000
350000
300000
434
250000
200000
369
267
249
150000
149
177
334
221
408
195
100000
123
50000
79
105
387
0
40
60
80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC142
Abundance
Average of 27.853 to 27.891 min.: RXN_LSCREEN_160207_035.D (-)
207
100000
90000
295
80000
70000
73
60000
50000
40000
30000
41
313
434
267
147
20000
10000
0
341
177
96
249
369
393
415
123
230
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
- 581 -
PVC143
Abundance
240000
Average of 29.750 to 29.831 min.: RXN_LSCREEN_060207_036.D (-)
432
220000
200000
180000
160000
140000
120000
100000
80000
60000
91
342
119
40000
20000
0
40
165
145
191
209
65
241 265
283
314
370
406
388
40 60 80 100120140160180200220240260280300320340360380400420440
m/z-->
PVC144
Abundance
Average of 30.677 to 30.758 min.: RXN_LSCREEN_060207_036.D (-)
57
280000
260000
240000
220000
200000
180000
160000
85
140000
120000
100000
80000
60000
40000
113
141
20000
0
40
60
169
197
239
221
267
309
351
393
330
369
290
421
449
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
Pentaerythritol tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate)
Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6tetramethyl-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
H3C
CH3
O
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(4ethylbenzylidene)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
CAS Number:
31570-04-4
Molecular weight:
646.9 g/mol
Classification
Aryl phosphite
Structure:
CH3
H3C
CH3
CH3
H3C
CH3
CH3
O
O
CH3
H3C
P
H3C
H3C
O
H3C
CH3
H3C
Legislative restriction(s):
Tris(2,4-di-t-butylphenyl)
Synoptic Document.
CH3
CH3
phosphite
H3C
is
CH3
listed
in
the
This substance is on SCF List 2.
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, CibaGeigy 82 0873 Feb. 1985).’
- 587 -
PENTAERYTHRITYL
PROPIONATE]
Synonyms:
TETRAKIS
[3-(3´,5´-DI-T-BUTYL-4-HYDROXYPHENYL)
Tetrakis
[methylene
hydroxyhydrocinnamate)] methane
(3,5-di-tert-butyl-4-
Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl)-4hydroxy2,2-Bis ((3-(3,5-bis (1,1-dimethylethyl)-4-hydroxyphenol)1-oxopropoxy) methyl)-1,3-propanediyl ester;
Pentaerythritol
tetrakis
hydroxyhydrocinnamate;
(3,5-di-t-butyl)-4-
Tetrakis
[methylene-3(3´,5´-di-t-butyl-4-hydroxyphenyl)
propionate] methane;
Pentaerythrityl
tetrakis
hydroxyphenyl) propionate]
CAS Number:
6683-19-8
Molecular weight:
1178 g/mol
Classification
Sterically hindered phenol
[3-(3´,5´-di-t-butyl-4-
Structure:
HO
t-Bu
t-Bu
t-Bu
OH
O
t-Bu
O
O
O
O
O
O
O
t-Bu
t-Bu
t-Bu
OH
HO
t-Bu
Legislative restriction(s):
Tetrakis
[methylene
hydroxyhydrocinnamate)] methane
Synoptic Document.
This substance is on SCF List 2.
- 588 -
(3,5-di-tert-butyl-4is listed in the
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] [2,2,6,6TETRAMETHYL-4-PIPERIDYL)
IMINO]
HEXAMETHYLENE
[(2,2,6,6TETRAMETHYL-4-PIPERIDYL) IMINO]]
Synonyms:
N,N´-Bis
(2,2,6,6-tetramethyl-4-piperidinyl)-1,6hexanediamine, polymer with 2,4,6-trichloro-1,3,5-triazine
and 2,4,4-trimethyl-1,2-pentanamine,
CAS Number:
70624-18-9
71878-19-8
Molecular weight:
Classification
Typically 2000 g/mol
Oligomeric hindered amine
Structure:
H3C
CH3 H
N
CH3
N
CH3
N
N
N
N
NH
H3C
N
CH3 H
CH3
tert.Oct
CH3
n
Legislative restriction(s):
Poly [[6-[(1,1,3,3-tetramethylbutyl) amino]-s-triazine-2,4diyl] [2,2,6,6-tetramethyl-4-piperidyl) imino]
hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] is
listed in the Synoptic Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘TDI: 0.05 mg/kg b.w. 3month oral dog and 3- and 6-month oral rat studies,
mutagenicity studies. (RIVM rep.89/678608/006 198904-11).’
A specific migration limit (SML) of 3 mg/kg has been
assigned.
- 590 -
POLY(4-HYDROXY-2,2,6,6-TETRAMETHYL-1-PIPERIDINE
BUTANEDIOIC ACID)
Synonyms:
ETHANOL-ALT-1,4-
Dimethyl succinate polymer with 4-hydroxy-2,2,6,6tetramethyl-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
piperidine polymer
CAS Number:
65447-77-0
Molecular weight:
Typically 3500 g/mol
Classification:
Polymeric hindered amine
hydroxy-1-hydroxyethyl
Structure:
CH3
O
H3C
O
N
O
CH3
O
CH3
Legislative restriction(s):
n
Dimethylsuccinate/tetramethyl hydroxy-1-hydroxyethyl
piperidine polymer is listed in the Synoptic Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘TDI : 0.5 mg/kg b.w. 90Day oral rat and dog studies, 2-year oral rat study. (HRC
report CBG 237/92271, 10 May 1983).’
A specific migration limit (SML) of 30 mg/kg has been
assigned.
- 591 -
ERUCAMIDE
Synonyms:
Erucic acid amide
Erucylamide
Docosenamide
13-Docosenamide
cis 13-Docosenamide
CAS Number:
112-84-5
Molecular weight:
337.6 g/mol
Classification:
Aliphatic amide
Structure:
NH2
O
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.
This substance is on SCF List 3.
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
Molecular weight:
358.6 g/mol
Classification:
Aliphatic carboxylic acid ester
Structure:
O
CH3
O
HO
OH
Legislative restriction(s):
Glycerol monostearate is listed in the Synoptic
Document.
This substance is on SCF List 1.
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
CAS Number:
471-34-1
Molecular weight:
100.1 g/mol
Classification:
Inorganic salt
Structure:
CaCO3
Legislative restriction(s):
Calcium carbonate is
Document.
- 594 -
not
listed in the
Synoptic
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
CAS Number:
38613-77-3
119345-01-6
Molecular weight:
991 g/mol
Classification:
Aryl phosphonite
Structure:
H3C
H3C
H3C
CH3
CH3
H3C
CH3
CH3
H3C
O
H3C
O
P
P
O
CH3
O
H3C
H3C
CH3
CH3
H3C
CH3
H3C
Legislative restriction(s):
CH3
CH3
CH3
H3C
H3C
CH3
Tetrakis (2,4-di-tert-butyl-phenyl) 4,4'-biphenylenediphosphonite is listed in the Synoptic Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘TDI: 0.3 mg/kg b.w. 90day oral rat study and mutagenicity studies. (Sandoz
report 1979).’
A specific migration limit (SML) of 18 mg/kg has been
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
CAS Number:
2082-79-3
Molecular weight:
Classification:
531 g/mol
Hindered phenol
Structure:
CH3
O
CH3
C18H37
H3C
O
HO
H3C
H3C
Legislative restriction(s):
CH3
Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate is
listed in the Synoptic Document.
This substance is on SCF List 2.
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. 3103-92).’
A specific migration limit (SML) of 6 mg/kg has been
assigned.
- 597 -
OLEAMIDE
Synonyms:
9-Octadecenamide
Oleic acid amide
Oleyl amide
CAS Number:
Molecular weight:
Classification:
301-02-0
281.5 g/mol
Aliphatic amide
Structure:
H3C
NH2
O
Legislative restriction(s):
Oleamide is listed in the Synoptic Document.
This substance is on SCF List 3.
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
CAS Number:
1317-80-2
13463-67-7
Molecular weight:
79.9 g/mol
Classification:
Inorganic oxide
Structure:
TiO2
Legislative restriction(s):
Titanium dioxide is listed in the Synoptic Document.
This substance is on SCF List 1.
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
CAS Number:
61791-14-8
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);
Molecular weight:
356.5 g/mol
Classification:
Aliphatic carboxylic acid ester
Structure:
O
HO
O
CH3
OH
Legislative restriction(s)
Glycerol monooleate is listed in the Synoptic Document.
This substance is on SCF List 1.
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
CAS Number:
68037-49-0
Molecular weight:
260 – 372 g/mol
Classification
Alkyl sulfonates
Structure:
O
R
O
S
-
O
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
dimethylethyl)-
2,2´-(2,5-thiophenyl)-bis-5-(1,1-
2,5-Bis (5-t-butyl-2-benzoxazol-2-yl) thiophene
CAS Number:
7128-64-5
Molecular weight:
430.6 g/mol
Classification:
Bis (benzoxazolyl) derivative
Structure:
O
N
S
CH3
N
H3C
O
CH3
CH3
H3C
CH3
Legislative restriction(s):
2,5-Bis(5'-tert-butylbenzoxazol-2-yl)thiophene is listed in
the Synoptic Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘TDI: 0.01 mg/kg b.w. 90day 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-hydroxym-tolyl)-propionate)
Tris(nonylphenyl)phosphite
Processing aids / flow
promoters
Di-(2-ethylhexyl) phthalate
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)-4hydroxy-, 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-5methyl-1,2-ethanediyl bis (oxy-2,1-ethanediyl) ester
Triethylene glycol bis (3-t-butyl-4-hydroxy-5methylhydrocinnamate)
Triethylene glycol bis (3-t-butyl-4-hydroxy-5methylphenyl) propionate
Triethylene glycol bis [3-(3-t-butyl-4-hydroxy-5methylphenyl) propionate
Ethylenebis (oxyethylene) bis (3-t-butyl-4-hydroxy-5methylhydrocinnamate)
CAS Number:
36443-68-2
Molecular weight:
586.8 g/mol
Classification
Sterically hindered phenol
Structure:
CH3
OH
CH3
O
CH3
O
H3C
O
O
CH3
O
H3C
O
HO
CH3
CH3
Legislative restriction(s):
Ethylenebis (oxyethylene) bis (3-t-butyl-4-hydroxy-5methylhydrocinnamate) is listed in the Synoptic
Document.
This substance is on SCF List 2.
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)
CAS Number:
26523-78-4
Molecular weight:
689.0 g/mol
Classification
Phosphite triester of nonyl phenol
Structure:
C9H19
O
P
H19C9
O
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
CAS Number:
117-81-7
Molecular weight:
390.6 g/mol
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.
This substance is on SCF List 2.
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-ethanediylbisOctadecanamide, N,N´-ethylenebisStearic acid, ethylenediamine diamide
CAS Number:
110-30-5
68955-45-3
Molecular weight:
593.0 g/mol
Classification
Diamide
Structure:
O
NH
H35C17
C17H35
NH
O
Legislative restriction(s):
N,N-Bis(stearoyl)ethylenediamide is listed in the Synoptic
Document.
This substance is on SCF List 3.
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
ether
glycol
p-1,1,3,3-tetramethylbutylphenyl
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
Legislative restriction(s):
n = 5 - 10
Polyethyleneglycol octylphenyl ether is listed in the
Synoptic Document.
- 610 -
This substance is on SCF List 9.
- 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
CAS Number:
2440-22-4
Molecular weight:
225.3 g/mol
Classification
Benzotriazole derivative
Structure:
HO
N
N
N
CH3
Legislative restriction(s):
2-(2’-Hydroxy-5’-methylphenyl) benzotriazole is listed in
the Synoptic Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘Group TDI: 0.5 mg/kg
b.w. for 2-(2'-hydroxy-3'-tert.butyl-5'-methylphenyl)-5chlorobenzotriazole, 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-1phenylethyl)phenol
Acetaldehyde scavanger
Hexanedioic acid polymer with 1,3benzenedimethanamine
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]-2Hbenzotriazole
2-(Benzotriazol-2-yl)-4,6-bis
phenol
(1-methyl-1-phenylethyl)
2-[2´-Hydroxy-3´,5´-bis
benzotriazole
(1-methyl-1-phenylethyl)]
CAS Number:
70321-86-7
Molecular weight:
447.6 g/mol
Classification
Benzotriazole derivative
Structure:
H3C
HO
CH3
N
N
N
H3C
H3C
Legislative restriction(s):
2-[2-Hydroxy-3,5-di-(1,1-dimethylbenzyl) phenyl]-2Hbenzotriazole is listed in the Synoptic Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘TDI: 0.025 mg/kg b.w. 90day 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
CAS Number:
25718-70-1
Molecular weight:
Not defined
Classification
Amide polymer
Structure:
O
H
OH
NH
NH
O
n
Legislative restriction(s):
Nylon MXD6 is listed in the Synoptic Document.
This substance is on SCF List 7.
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
CAS Number:
147-14-8
Molecular weight:
576.1 g/mol
Classification
Phthalocycanine complex
Structure:
N
NH
N
Cu
N
N
N
NH
N
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
CAS Number:
68109-88-6
Molecular weight:
631.4 g/mol
Classification
Organotin compound
Structure:
O
O
CH3
H3C
O
O
O
O
O
Sn
C8H19
C8H19
O
Legislative restriction(s):
Dioctyltin bis(erthylmaleate) is listed in the Synoptic
Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘Group-TDI: 0.0006 mg/kg
bw (as Sn) for all di-n-octyltin derivatives. See references
for 50480.
http://europa.eu.int/comm/food/fs/sc/scf/out41_en.pdf’
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-4stannatetradecanoate
8-Oxa-3,5-dithia-4-stannatetradecanoic acid, 10-ethyl4,4-dioctyl-7-oxo-, 2-ethylhexyl ester
CAS Number:
15571-58-1
Molecular weight:
751.8 g/mol
Classification
Organotin compound
Structure:
CH3
C 4H 9
O
O
S
O
S
Sn
C 8H 19
C 8H 19
O
H3C
Legislative restriction(s):
C 4H 9
Dioctyltin bis(ethylhexyl mercaptoacetate) is listed in the
Synoptic Document.
This substance is on SCF List 2.
The EFSA/SCF opinion states ‘Group-TDI: 0.0006 mg/kg
bw (as Sn) for all di-n-octyltin derivatives. See references
for 50480.
http://europa.eu.int/comm/food/fs/sc/scf/out41_en.pdf’
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
CAS Number:
8013-07-8
Molecular weight:
Not defined
Classification
Epoxy compound
Structure:
O
H3C
O
O
O
O
O
O
O
O
H3C
O
O
H3C
O
Legislative restriction(s):
ESBO is listed in the Synoptic Document.
This substance is on SCF List 2.
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 -
O
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.
For materials and articles intended for or brought into
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.
For materials and articles intended for or brought into
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
Molecular weight:
284.5 g/mol
Classification
Fatty acid
Structure:
O
OH
H3C
Legislative restriction(s):
Stearic acid is listed in the Synoptic Document.
This substance is on SCF List 1.
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
ester
acid,
tributyl
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
Molecular weight:
402.9 g/mol
Classification
Aliphatic ester
Structure:
O
O
H3C
O
CH3
O
CH3
O
CH3
O
O
O
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; 2generation 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.
http://europa.eu.int/comm/food/fs/sc/scf/out10_en.pdf’
- 624 -
PARAFFIN WAX
Synonyms:
Hard paraffin
Paraffin waxes
Paraffin wax fume
Petroleum wax, crystalline
Poly (methylene) wax
CAS Number:
8002-74-2
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 centistokes) at 100 °C
11
×
10–6
- Average molecular weight not less than 500.”
- 625 -
m2/s
(=
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,
CAS Number:
14807-96-6
Molecular weight:
294 g/mol
Classification:
Inorganic salt
Structure:
3MgO.4SiO2.H2O
Legislative restriction(s):
Talc is listed in the Synoptic Document
This substance is on SCF List 1.
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
CAS Number:
557-05-1
Molecular weight:
632.2 g/mol
Classification
Zinc salt of stearic acid
Structure:
O
Zn
H35C17
O
-
2
Legislative restriction(s):
Zinc stearate is not listed in the Synoptic Document.
- 628 -