harnessing the power of ccs for routine screening applications on the unifi informatics platform
TRANSCRIPT
Harnessing the Power of CCS for Routine
Screening Applications on the UNIFI Informatics Platform
Cristina Nerín I3A, Dept. Anal. Chem. University of Zaragoza
(Spain) [email protected]
1
Outline
• Introduction: Food Packaging Materials – Migration – IAS and NIAS – Analytical protocols
• Case Study 1: PSA • Case study 2: NIAS and set-off migration (1) • Case study 3: NIAS and set-off migration (2) • Risk assessment
2
FOOD PACKAGING MATERIALS
3
Cardboard packaging
Material A + Printing Inks + Lacquer/varnish Material A + Adhesive + material B + Printing inks + Lacquer/varnish Adhesives directly applied on food: PSA
High Barrier Materials (multilayers)
Monomaterial/monolayer Multilayer&multimaterial
food
MIGRATION FROM PACKAGING TO FOOD
TOXIC EFFECTS IN FOOD CONSUMERS
CHANGES IN FOOD SENSORY PROPERTIES
PHYSICO-CHEMICAL CHANGES ON PACKAGING
adhesive printing ink
food
K,D
Multilayer packaging Monolayer packaging
SET OFF (ink transference)
Direct contact Pressure
From manufacturing processes
NIAS NON INTENTIONALLY ADDED SUBSTANCES
Degradation processes: • Polymer degradation • Additives degradation
Impurities of raw materials
Reaction Products
Contaminants
IAS INTENTIONALLY
ADDED SUBSTANCES
Polymer additives: antioxidants, flame retardants, UV absorbers, …
Additives from adhesives, varnishes, printing inks
Residual monomers, catalysts
MIGRANTS ORIGIN
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Well known NIAS
2,4-DTBP
ADDITIVES DEGRADATION Irgafos 168 (antioxidant)
Formaldehyde and acetaldehyde
(off-flavours)
P O O
O
P O
O
P O
+
+
[ H 2 O ]
O OOP
OO O
OP[O]
POLYMER DEGRADATION PET bottles
[Dabrowska et al. Food Addit. Contam. 20 (2003) 1170] [Bach et al. Water Res. 46 (2012) 571]
[Burman et al. J. Chromatogr. A 1080 (2005) 107] [Alin et al. J. Agric. Food Chem. 59 (2011) 5418] [Bertoldo et al. Polymer 45 (2004) 8751]
Factors that can affect: temperature oxygen irradiation
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NIAS
NEOFORMED COMPOUNDS
Epoxy phenolic coatings: BADGE
BADGE-H2O BADGE-2H2O BADGE-HCl
+H2O, +HCl
BY-PRODUCTS
Polyurethane adhesives
Isocyanates Polyols +
+H2O
Primary aromatic amines
[Aznar et al. J. Chromatogr. A 1216 (2009) 5176]
[Sendon Garcia et al. J. Chromatogr. A 1032 (2004) 37] [Perez-Lamela, et al. Int. J. Environ. Anal. Chem. 82 (2002) 123]
PU ADHESIVES LACTONES
lactones
Migration test
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C. Nerin et al. Scientific reports (NATURE) http://www.nature.com/srep/2014/140509/srep04913/full/srep04913.html F. Isella, E. Canellas, O. Bosetti, C. Nerin, Journal of Mass Spectrometry, 48, 4, 430–437, April 2013 - 10.1002/jms.3165, 2013 Juliana S. Félix, Francesca Isella, Osvaldo Bosetti, Cristina Nerín Analytical and Bioanalytical Chemistry, Volume 403, Number 10 (2012), 2869-2882
Analytical Challenges
• Sample treatment developments
• Decision about the analytical procedure: Usually working with “blind samples” (no information about the composition or the likely migrants). What is the target?
• Identification of unknowns
• Origin of the migrants: responsibility!!
• Low concentration of many migrants
• Complex analysis of food
• Analytical artifacts
POLYMER
DirectAnalysis Migration Test
Tenax Liquid FoodSimulants
SPME LLE LLMEHSThermal
DesorptionSolid / Liquid
extraction
HS SPMEPurge
&Trap
HS: Headspace SPME: Solid Phase Microextraction LLE: Liquid – Liquid extraction LLME: Liquid – Liquid microextraction
General scheme for sample treatment MIGRATION CELL
10
Polymer Food simulant
EU/10/2011
Decision tree for the analytical procedure in NIAS identification
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L C - M S (Q T OF ) GC - M S
-
C on f i r mat i on b y St a nd a r d
Y es
GC - M S ( Q T O F )
No
Y es
No
Q u a n t i f i c a t i o n
C on f i r mat i on b y f r a g m e n t a t i o n
C on f i r mat i on b y Sta nd a r d
Y es No
Y es
S e l e c t i o n o f c a nd i d a te s t r u c t u r e
• C h e m i c al d a t ab a s e s • Sa m ple in f or m a t i o n • Bibli o gra p hi c s e ar c h • C a ndid a t e prop e r t i e s
S e l e ct i on o f p a r e n t i on e m p i r i c a l f o r m u l a
• Ele m e n t s s ele c t i o n • M a s s t olera n c e • I s o t o pi c f it
I d e n t i f i c a t i on b y :
• N I S T libr a ry • Ko v a t s in d ex
ANA L Y SIS
No
Volatiles Non
volatiles
C. Nerin*, P. Alfaro, M. Aznar, C. Domeño Anal. Chim. Acta. Volume 775, 2 May 2013, Pages 14–24 DOI:10.1016/j.aca.2013.02.028. 2013
Examples
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Reprotoxic compounds identified in plastic bags for semen dosis
By-products resulting from interaction between ingredients in common adhesives
NIAS from adhesives in high barrier materials
Contamination of food from Set-off of printing inks
Oligomers and NIAS in Polymers
NIAS from active packaging materials
Degradation compounds from gamma irradiation on packaging materials
Degradation compounds from interaction with the packaged product
Migrants from the packaging in food
Identification of volatiles by GC-MS (EI)
Identification of volatiles by APGC-MS (TOF)
1
2
3 Comparison of both techniques
APGC-MS-QTOF versus GC-MS-Q
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Migration of Volatile compounds from PSA adhesives
Case study 1
4 Specific migration analysis and Risk Asssessment
Case study 1
Migration from Pressure Sensitive Adhesive
GC-MS
APGC-MS-QTOF
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Function 1 cone voltage 30 V
Function 2 High energy30 v in cone
voltage and a collision ramp energy in the collision cell
from 20 to 40 v
Migration from Pressure Sensitive adhesive
Case study 1
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Migration from Pressure Sensitive adhesive
Case study 1
Phosphorous was confirmed by ICP-MS
Migration from Pressure Sensitive adhesive
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Case study 1
Migration through pork intestine to isoctane
adhesive Smoking thin paper
tenax
Migration from Pressure Sensitive adhesive
Case study 1
Canellas,E., Vera, P, Nerín. C. J. Mass Spectrometry, 2014, 49. 1181
Migration of PSA adhesives in meat(longaniza) and simulants
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Case study 1
Dicyclohexylphosphino isomer3(III)
Set D
PET: polyethylene terephtalate OPP: Oriented Polypropylene Al: aluminum PE: polyethylene
Case study 2
1 2 3 4
Migration tests with food Simulants
Set D / EtOH 95% Material 2
Set D / Tenax® Material 2
Case study 2
PET
AL PE
1A
Food
SCR1
INK PET AL
PE
Food
Case study 2
INK PET AL PE
SCR1
Food
PET INK
AL PE
4A
LAQUER MATT
Food
Case study 2
Ink migrants (ID_code) M.2 Molecular
formula Candidates Mat. 3 Mat. 4
3.90_217.1080 2 C10H16O5 Cyclic polyester ↓↓ ↓↓ 4.62_285.1315 1 C12H22O6 Adipate structure ↓↓ ↓↓ 5.35_251.1260 2 C12H20O4 Cyclic polyester ↓(IM3=40%IM2) ↓↓ 5.44_453.1770 2 C22H28O10 Cyclic polyester ↓↓ ↓↓ 5.50_473.1448 1 C24H24O10 Cyclic polyester ↓↓ ↓↓ 5.71_337.1627 1 C16H26O6 Di(tetrahydrofurfuryl)adipate ↑(IM3=150%IM2) ↓↓ 6.50_273.2067 3 C15H28O4 Dibutyl pimelate ↓↓ ↓↓ 6.50_259.1911 3 C14H26O4 Diethyl sebacate ↓↓ ↓↓ 6.82_389.1118 <1 C14H20N4O7S n.i. ↓↓ ↓↓ 6.97_403.2334 3 C20H34O8 ATBC ↓↓ ↓↓ 7.05_287.2230 3 C16H30O4 Dipropyl sebacate ↓↓ ↓↓ 7.19_297.2412 1 C16H34O3 n.i. ↓↓ ↓↓
7.22_341.2655 1 C18H38O4 Triethylene glycol
monododecyl ether ↓↓ ↓↓
7.23_385.2928 1 C20H42O5 Tetraethylene glycol monododecyl ether
↓↓ ↓↓
7.36_315.2549 3 C18H34O4 Dibutyl sebacate = = 7.62_343.2855 3 C20H38O4 Glycol ricinolate = ↓(IM4=20%IM2) 7.80_371.3174 2 C22H42O4 Di-hexyl sebacate ↑(IM3=200%IM2) ↓(IM4=15%IM2)
Set D / Tenax®
Mat
. 1
Mat
. 2
Mat
. 3
Mat
. 4
Table 1: Migrants coming from ink due to set-off (material 2), I (1: low intensity, 2: medium intensity, 3: high intensity), molecular formula, candidates and relative changes of intensity in migration from materials 3 and 4 (↓↓ total decrease, ↓partial decrease, = same intensity)
Case study 2
PCA of migration data
-100
-80
-60
-40
-20
0
20
40
60
80
100
0010001-
t[2]
t[1]
Scores Comp[1] vs. Comp[2] colored by Sample Group
1A1A1A1A1A1A1A1A1A
2A
2A2A
2A
2A
2A2A
2A
2A
2A
2A
2A
3A3A3A3A3A3A
3A3A3A
4A
4A4A
4A4A4A
4A
4A
4A
4A4A4A
SCR1SCR1SCR1
SCR1SCR1SCR1SCR1SCR1
SCR1SCR1SCR1
PET AL
PE
1A
Food
INK PET AL
PE
SCR1
Food
INK PET
AL PE
3A
LAQUER MATT
Food
PET INK
AL PE
4A
LAQUER MATT
Food
INK PET
AL PE
2A
LAQUER GLOSS
Food
Case study 2
Case study 2
Identification by RT and MS fragments
Identification by IM (CCS)
Candidates
CCS
Pure standards
Case study 2
OPP OPP INK
Migrats from ink Elemental composition Molecular formula Candidates CCS
4.93_299.1108 C12H20O7Na C12H20O7 Citric acid triethyl ester 103.03
5.63_285.2909 C17H37N2O C17H36N2O Schercodine L
(lauramidopropyl-dimethylamine) 120.19
5.92_271.1885 C13H28O4Na C13H28O4 Tripropyleneglycol monobutyl
ether 99.69
5.96_299.1835 C14H28O5Na C14H28O5 Triethylene glycol caprylate No standard
6.09_313.3217 C19H41N2O C19H4ON2O Schercodine M
(Myristamidopropyl-dimethylamine)
No standard
6.39_343.2965 C19H39N2O3 C19H38N2O3 Lauraimidopropyl betaine No standard
6.98_425.2151 C20H34O8Na C20H34O8 Acetyltributylcitrate (ATBC) 137.45
Food simulant Food simulant
Case study 3
DIRECT ANALYSIS OF SAMPLE 1
DESI-TOF
ATBC
m/z 285.29
Schercodine L
Case study 3
m/z 285.3
m/z 425.2 m/z 149.1
Sample 2
Schercodine L
DESI-TOF Case study 3
Phthalate?
ATBC
TOXICITY REPORTS
EUROPEAN LEGISLATION (EU/10/2011)
What to do after identification?
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NO TOXICITY DATA
Threshold of Toxicological Concern (TTC) approach (not suitable for carcinogenic, mutagenic or teratogenic compounds)
CRAMER RULES
RISK ASSESSMENT OF NIAS
NATIONAL LEGISLATION
Threshold of Toxicological Concern (TTC)
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TOXICITY CLASIFICATION-Cramer rules (Toxtree v1.51)
Class I (Low) <1.8 mg/person/day Class II (Medium) <0.54 mg/person/day Class III (High) 0.09 mg/person/day
BHT
EDI (Estimated Dayly Intake) (mg/person/day)= Mig (mg/Kg) x 3 Kg /day/person x CF
Migration estimation
Where • Estimated Daily Intake is the Cramer value • Mig: Migration limit (proposal) • 3Kg/1Kg is the daily food intake (including beverage) • CF is the fraction of the daily diet expected to be in contact
with a specific packaging material (e.g.for adhesives this is 0.14).
EDI (mg/person/day)= Mig (mg/Kg) x 3 Kg* /day/person x CF
Consumption factors exist in FDA but not in Europe
35 GUIA GROUP, UNIVERSITY OF ZARAGOZA, SPAIN
Acknowledgements
Research Projects:
• SAFEMTECH (IAPP-Marie Curie) • SAENMA (AGL-2012) • MAGAPOR • MIGREFILMS • MIGRESIVES (EU) • NANOFLEXIPACK • R&D&i with several companies • ……… • Collaboration with Waters