Analysis of chemical trace contaminants in foods ... · Research Joint Unit GENIAL “Ingénierie...
Transcript of Analysis of chemical trace contaminants in foods ... · Research Joint Unit GENIAL “Ingénierie...
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V. Camel – Webinar, 15 December 2016
Valérie CAMELProfessor
AgroParisTech - Department of Food Science and TechnologyResearch Joint Unit GENIAL “Ingénierie Procédés Aliments” (INRA, AgroParisTech)
Analysis of chemical trace contaminantsin foods: performance and limits
V. Camel – Webinar, 15 December 2016
Content of the course
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Introduction Analyticalapproach
Performance and limits
Future challenges
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Chemical hazards in foods on covers!
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Introduction Analyticalapproach
Performance and limits
Future challenges
March 2011
October 2013
January 2011
December 2016
October 2016
June 2015
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Chemical contaminants or residues
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Introduction Analyticalapproach
Performance and limits
Future challenges
PesticidesVeterinary residues
Residuesfrom authorized
treatments
Natural substances
Heavy metalsMycotoxinsPhycotoxins
Environmental contaminants
POPs (dioxins, PCBs,…)PAHsHeay metals
Contaminants from materials in contact
Contaminants from processing
Acrylamide, furanPAHs, HAAs
Bisphenol A
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European regulation on its way…
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Introduction Analyticalapproach
Performance and limits
Future challenges Maximal Residue Limits
(MRLs)Pesticides :regulation 1107/2009/EC + 283/2013/EC & 284/2013/EC
Veterinary residues:regulation 2377/90/EC
Maximal Residue Limits (MRLs) + non-authorized substances
Environmental contam.: regulation 1881/2006/EC + 420/2011/EC (Pb,Cd, Hg, Sn, dioxins, DL-PCBs, BaP) + 835/2011/EC (PAHs)
Maximum Levels (MLs)
Food contact materials:regulation 1935/2004/EC+10/2001/EC & 2016-1416/EC (plastics)
Specific Migration Limits (SMLs) (plastics)
Processing contam.:regulation 1881/2006/EC (3-MCPD)+ recommandations (acrylamide)
Maximum Levels (MLs) +« Guide » values
Mycotoxins:regulation 1881/2006/ECMaximumLevels (MLs)
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All operators are responsible for food safety
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Introduction Analyticalapproach
Performance and limits
Future challenges
Processedmaterial
Packagedfood
Distributedfood
Consumedfood
Rawmaterial
Primary production
StoragePackaging
Distribution
Storage, cooking
Cattle feed
Processing
Integrative approach:« From fark to fork »« From stable to table »
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Sampling and analysis: key issues!
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Introduction Analyticalapproach
Performance and limits
Future challenges
Samples
ü EU productionü Importationsü Exportations
ü Official routine labsü National Reference Labsü EU Reference Labs
Analyticalresults
Validated methods
oMonitoring plansoControl plans
RASFF
Risk assessment
Regulation compliance
EU recommendations for sampling / several contaminants
V. Camel – Webinar, 15 December 2016
Ex.: 2015 RASFF notifications
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Introduction Analyticalapproach
Performance and limits
Future challenges
RASFF: Rapid Alert System for Food and Feed
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V. Camel – Webinar, 15 December 2016
Food (and feed) matrices are highly complex…
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Introduction Analyticalapproach
Performance and limits
Future challenges
MacromolecularMacromolecularcompounds:compounds:-- proteinsproteins-- polyosidespolyosides
WaterWater
Fat Fat mattermatter
Minerals
Food structureFood structure
Water content?Lipid content?Pigments? Others?
Water content?Lipid content?Pigments? Others?
Free or boundcontaminants?Free or boundcontaminants?
Heterogeneity?Variability?Heterogeneity?Variability?
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…and contaminants present at low levels!
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Com
poun
d le
vel (
in m
assi
c fr
actio
n)
1
10-3
10-6
10-9
10-12
10-15
Usu
al le
vel e
xpre
ssio
n
100%
0.1%
1 ppm
1 ppb
1 ppt
Maj
or
com
poun
ds
Min
or
com
poun
ds
Trac
e co
mpo
unds
Ultr
a-tr
aces
co
mpo
unds
Lim
its o
f an
alyt
ical
m
etho
ds
ppt : part per trillion(ng/L or ng/kg)
ppm : part per million(mg/L or mg/kg)
ppb : part per billion(µg/L or µg/kg)
Introduction Analyticalapproach
Performance and limits
Future challenges
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V. Camel – Webinar, 15 December 2016
From sampling to analytical results…
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Introduction Analyticalapproach
Performance and limits
Future challenges
Sampling
Sample ResultsSample treatment Analysis Data
treatment
THE ANALYTICAL PROCESS
Sub-sample
Reliable results:ü Validated methodü Lab proficiency
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The analytical process
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Introduction Analyticalapproach
Performance and limits
Future challenges
Samplepre-treatment Extraction Clean-up
LIQUID LIQUID foodsfoods
SOLID SOLID foodsfoods
HomogeneizationFreez-drying
FiltrationCentrifugationProtein precipitation
USE, MAEPLE, MSPD
LLE, SPESPME, SBSE
LLE, SPEGPC
GC-MS(/MS)LC-MS(/MS)
Target compounds
analysis
Data treatment
IdentificationQuantification
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New techniques have merged over years
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Introduction Analyticalapproach
Performance and limits
Future challenges
Gallo and Ferranti. J. Chromatogr. A 1428 (2016) 3
LC-MSUPLCHRMS
Very fast acquisitionImproved capabilityHigh sensitivity
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Illustration of the analytical approach
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Introduction Analyticalapproach
Performance and limits
Future challenges
Gallo and Ferranti. J. Chromatogr. A 1428 (2016) 3
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In practice: target oriented methods
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Introduction Analyticalapproach
Performance and limits
Future challenges
Betsou et al. Trends Anal. Chem. 66 (2015) 32
A priori known contaminants
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European Commission (2016)
Introduction Analyticalapproach
Performance and limits
Future challenges
Food categories are also targeted
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Validation of target-oriented methods
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Introduction Analyticalapproach
Performance and limits
Future challenges
1- Confirmation
Target contaminant(s) in real samples
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Matrix effects?
Expected tR
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Target analysis: 1- Compound confirmation
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Introduction Analyticalapproach
Performance and limits
Future challenges
Hird et al. Trends Anal. Chem. 59 (2014) 59
Ions-selected time windows adjusted to target compounds retention times
üCheck tR stabilityüSelectivity and
sensitivity
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Ex: compound confirmation
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ü Retention timeü Exact mass (HR)ü Fragmentsü Isotopic pattern
Introduction Analyticalapproach
Performance and limits
Future challenges
Cotton et al. J. Agric. Food Chem. 62 (2014) 11335
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Ex: MS vs HRMS for target confirmation
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Introduction Analyticalapproach
Performance and limits
Future challenges
UPLC-MS/MS MRM mode 299 ->
UPLC-HRMS Exact mass
Lacina et al. J. Chromatogr. A 1262 (2012) 8
Expected tR
Increased selectivity with
HRMS
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Validation of target-oriented methods
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Introduction Analyticalapproach
Performance and limits
Future challenges
1- Confirmation
Target contaminant(s) in real samples
2- Quantification
LOQ (compliance with MRLs)TruenessPrecision
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Matrix effects?
Expected tR
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Introduction Analyticalapproach
Performance and limits
Future challenges
Target analysis: 2- Quantification
x Reference value X
Single result Zi
Bias
Mean value Z
Performance criteriaü LOQü Recoveryü Truenessü Precision
LOQ: level for S/N= 10
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Introduction Analyticalapproach
Performance and limits
Future challenges
Ex: LOQs of labs for acrylamide analysis
EFSA Journal 10 (2012) 2938
ü Food typeü Lab method
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Introduction Analyticalapproach
Performance and limits
Future challenges
2- Quantification – Matrix effects
Signal
Effects of ion suppression or signal enhancementEffects of ion suppression or signal enhancement
Fernandez-Alba et al. Trends Anal. Chem. 27 (2008) 973
LC-MS
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Strategies to limit matrix effects
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Introduction Analyticalapproach
Performance and limits
Future challenges
Stable-isotope labelled int. std
Improve clean-up
MS/MS or HRMS analysis
Improve separation
Dilute extract
Ext. matrixmatch calibration
V. Camel – Webinar, 15 December 2016
Ex: HRMS analysis of target pesticides
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Extracted ion (exact mass)
LOD : 0,04 –150 µg/kg
LC-TOF-MS Expected tR
Introduction Analyticalapproach
Performance and limits
Future challenges
Ferrer et al. J. Chromatogr. A 1175 (2007) 24
Full scan
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Introduction Analyticalapproach
Performance and limits
Future challenges
Dzuman et al. Anal. Chim. Acta 863 (2015) 29
Ex: matrix match calibration in LC-HRMS analysis
Changes in relative intensityof fragments
Changes in relative intensityof fragments
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Validation of target-oriented methods
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Introduction Analyticalapproach
Performance and limits
Future challenges
1- Confirmation
Target contaminant(s) in real samples
3- Applicability
Concentration rangeType of food(s)
2- Quantification
LOQ (compliance with MRLs)TruenessPrecision
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Matrix effects?
Expected tR
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Recent and future challenges
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Introduction Analyticalapproach
Performance and limits
Futures challenges
Identification of new contaminants?
Simultaneous analysis of targetmulti-class contaminants?
Analysis of non target contaminants?
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Multi-residue / multi-class target analysis…
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Introduction Analyticalapproach
Performance and limits
Futures challenges
Non selective extractionNo clean-upEfficient separationMS/MS, HRMS
Dzuman et al. Anal. Chim. Acta 863 (2015) 29 – Danezis et al. . Anal. Chim. Acta 942 (2016) 121
323 pesticides55 mycotoxins11 plant toxins
LOQs < 10 µg/kg
Most LOQs in range 1-10 µg/kg
28 compounds
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…towards non-target approaches?!Introduction Analyticalapproach
Performance and limits
Future challenges
Masia et al. Anal. Chim. Acta 936 (2016) 40
Data dependent acquisition
Data independent acquisition
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Introduction Analyticalapproach
Performance and limits
Future challenges
Comparison with blanks and controlsRemoval of noise and irrelevant peaks
Identification of « non target » compounds
Retrospective screening
Database
Bletsou et al. Trends Anal. Chem. 66 (2015) 32
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Conclusion
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PastPast PresentPresent Future?Future?
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Contact: [email protected]
Evard et al. Anal. Chim. Acta 942 (2016) 40