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ยฉ2016 Waters Corporation 1
Routine Quantification of Multi-Residue
Pesticides in Food Matrices using
UPLC and APGC coupled to MS/MS
ยฉ2016 Waters Corporation 2
Overview
๏‚ก Challenges and method requirements for multi-residue analysis
๏‚ก Single instrument platform for LC and GC amenable pesticides
๏‚ก Sample preparation and analysis workflow
๏‚ก Acquisition modes โ€“ MS/MS, RADAR, PICS
๏‚ก Quanpedia database - Pesticides, metabolites, toxins and other
contaminants
๏‚ก Collaboration (Nofa Lab) - Validation study for analysis of 460
pesticides in 10 different food commodities using APGC-MS/MS
๏‚ก Summary and Conclusions
ยฉ2016 Waters Corporation 3
Challenges in Multi Residue Pesticide
Analysis of Food Products
Changing
Legislation
Demanding
Performance
Multitude of
Food Types
Variety of
Pesticides
ยฉ2016 Waters Corporation 4
๏‚ก High throughput: Generic QuEChERS clean up
๏‚ก Quantification & confirmation: gold standard MS/MS
๏‚ก Sensitivity: 0.01 mg/kg
๏‚ก Method robustness: System up time, instrument
maintenance
Multi Residue Pesticides in Food
Method Requirements
Food
product
Representative
extract
GC with MS/MS detection
LC with MS/MS detection
ยฉ2016 Waters Corporation 5
Xevo TQD
Xevo TQ-S
XEVO Tandem Quadrupole Systems
Xevo
TQ-S micro
๏‚ก Routine UPLC-MS/MS
๏‚ก RADAR acquisition mode
๏‚ก Universal ion source
๏‚ก Compact with high sensitivity
๏‚ก RADAR acquisition mode
๏‚ก Universal ion source
๏‚ก Fast data acquisition
๏‚ก Xtended Dynamic Range
๏‚ก Ultimate sensitivity
๏‚ก RADAR acquisition mode
๏‚ก Universal ion source
๏‚ก ScanWave Enhanced
product ion scanning
Ultimate sensitivity
and reliability
Sensitive, reliable
and compact
Robust, reliable
and proven
ยฉ2016 Waters Corporation 6
Extended Dynamic Range
๏‚ก Provides up to 6 orders of linear dynamic range
๏‚ก Easier to transfer methods from other instruments with higher or lower
sensitivities
๏‚ก Accessible sensitivity
0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80
%
0
1x, 1 ng
1x, 100 pg
10x, 10 pg
82x, 1pg
876x, 100 fg
10,000x, 10 fg
10,000x magnification, 1 fg
ยฉ2016 Waters Corporation 7
Increased Capability
LC and GC Workflow on one MS Platform
UPLC-MS/MS APGC-MS/MS
Quantitative & Confirmatory Analysis
LC and GC with XEVO TQ-S micro
ยฉ2016 Waters Corporation 8
Quantitative & Confirmatory Analysis
LC and GC with XEVO TQ-S micro
10 ยตg/kg
Compound name: Pyracarbolid
Correlation coefficient: r = 0.999741, r^2 = 0.999482
Calibration curve: 2921.65 * x + -539.66
Response type: External Std, Area
Curve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None
Standard Addition Concentration : -0.184711
ppb
-0 10 20 30 40 50 60 70 80 90 100
Response
-0
100000
200000
ppb
Residual
-2.00
0.00
2.00
Compound name: Pyracarbolid
Correlation coefficient: r = 0.999741, r^2 = 0.999482
Calibration curve: 2921.65 * x + -539.66
Response type: External Std, Area
Curve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None
ppb
-0 10 20 30 40 50 60 70 80 90 100
Response
-0
100000
200000
ppb
Residual
-2.00
0.00
2.00
ยฉ2016 Waters Corporation 9
Generic Cleanup with QuEChERS
Homogenisation
15 g sample
DisQuE extraction
15 mL 1 % acetic acid in ACN
Centrifuge
3500 RPM 5 min
DisQuE Tube 2
186004832
Dilute
1 in 10 in water
Solvent Exchange
500 ยตL ethyl acetate
APGCUPLC
ยฉ2016 Waters Corporation 10
UPLC-MS/MS
๏‚ง Diluted QuEChERS extract, spiked with LC
pesticide mix
๏‚ง LC multi-residue pesticide mix ~204
compounds
๏‚ง Solvent curve - 1 to 500 ppb
๏‚ง Matrix match spiked curve - 1 to 500 ppb
LC - 204 pesticides mix
Experiments
APGC-MS/MS
๏‚ง After solvent exchange of QuEChERS
extract, spiked with GC pesticide mix
๏‚ง GC multi-residue pesticide mix ~203
compounds
๏‚ง Solvent curve โ€“ 0.1 to 100 ppb
๏‚ง Matrix match spiked curve โ€“ 0.1 to 100 ppb
๏‚ง Accurately detect and quantify multi-residue
pesticides in a wide range of fruits, vegetables,
and other commodities by UPLC-MS/MS
๏‚ง Full kit contains 204 pesticides, formulated and
grouped for maximum long-term stability
๏‚ง Optimized multi-residue pesticide method with
UPLC conditions and MS/MS transitions available
ยฉ2016 Waters Corporation 11
Determine Sample Prep Efficiency
๏‚ก What is RADAR?
โ€“ Rapid electronics allow instrument to switch between MRM & full scan
โ€“ Added information can be gained from full scan data in routine analyses
โ€ข Intelligent decision making
โ€ข Improves method development
โ€ข Monitor matrix components
โ€ข Detect un-targeted adulterants
๏‚ก How do I set it up on the instrument?
- Parallel MRM with full scan data acquisition
ยฉ2016 Waters Corporation 12
Grape
Avocado
Marjoram
Ginger
Ultra Trace Analysis:
Sample Complexity
Xevo TQ-S
ยฉ2016 Waters Corporation 13
Ultra trace analysis: Matrix effects
DisQuE Ginger QC extract
pesticides @ 0.01 mg/kg (10 ppb)
Cyromazine
Simetryn
Atrazine
Azinphos
-ethyl
Poor peak shape
Low calculated recoveries
High Matrix background
Xevo TQ-S
ยฉ2016 Waters Corporation 14
Ultra trace analysis:
Reduced matrix effects (10x Dilution)
Cyromazine
Simetryn
Atrazine
Azinphos
-ethyl
10 x dilution of Ginger extract
All peaks detected, recoveries good
Reduced Matrix background
by 10X dilution
Improved peak shape
-54%
-58%
-47%
Reduced ion suppression
ยฉ2016 Waters Corporation 15
Multi-Residue Pesticide Analysis in Green Grapes
Using UPLC-MS/MS
ยฉ2016 Waters Corporation 16
UPLC-MS Conditions
LC System: Waters ACQUITY H-Class
Column: ACQUITY UPLC BEH C18 2.1 x 100 mm, 1.7 ยตm
Column Temp: 45 หšC
Flow Rate: 0.450 mL/min
Injection volume: 10 ยตL
Mobile Phase A: 10mL of 1M ammonium acetate (pH5.0) + 990mL Water
Mobile Phase B: 10mL of 1M ammonium acetate (pH 5.0) + 990mL MeOH
Gradient:
Min %A %B Curve
Initial 98.0 2.0
0.25 98.0 2.0 6
12.25 1.0 99.0 6
13.00 1.0 99.0 6
13.01 98.0 2.0 6
17.00 98.0 2.0 6
MS System: Xevo TQ-S micro
Capillary (kV): 1.0
Source Temp.: 150ยฐC
Desolvation Temp.: 500ยฐC
Desolvation Gas Flow: 1000 L/Hr
MRM Transitions: TQ-S micro Quanpedia
ยฉ2016 Waters Corporation 17
โ€ข Is my system ready, does it satisfy lab quality requirements?
Set-up and check analytical system
Automated Quan Workflow:
From System Setup to Data Processing
โ€ข The QuanPediaโ„ข database allows for efficient method management
Select or create LC-MS/MS method
โ€ข TargetLynx XS streamlines automated quantitative data review and reporting
Comprehensive data processing and review
โ€ข Trending inter- and intra-batch QC and sample results over time is easy
with TrendPlot
Compare data day to day, week to week
โ€ข Automated real-time QC checking with QCMonitor prevents wasting
valuable samples
Critical QC Information Delivered Real Time
ยฉ2016 Waters Corporation 18
IntelliStart: Ready to Use System
๏‚ก IntelliStart
๏‚ก In-built Fluidics
๏‚ก Automated delivery
of reference
solutions
๏‚ก Automated flow
switching
ยฉ2016 Waters Corporation 19
Quanpedia for XEVO TQ-S micro
๏‚ก Compound database includes
โ€“ LC-MS/MS method files (UPLC and MRM conditions)
โ€“ TargetLynx quantification
โ€“ PICS
โ€“ Options for modifying and optimizing methods
๏‚ก Analyses include:
Alternaria toxins Diquat and Paraquat Patulin Polyphenols
Aminoglycosides Endocrine disrupting compounds Perfluorinated Progestogens
Amphetamines Glyphosate and AMPA Pesticide polarity switching Quinolones
Androgens and
progestogens
Heterocyclic amines Pesticide screening Sudan dyes 1
Anthelminitics Hormones Pesticides (APEDA- India) Sulfonamides
Antibiotics Japanese positive list Pesticides 375 Tetracyclines
Avermectins Marine biotoxins Pesticides in baby food Thyreostats
Beta agonists Melamine
Pharmaceutical and personal
care products
Triarylmethane dyes
Bisphenol Mycotoxins Pharmaceuticals
Triarylmethane dyes and
metabolites
Chloramphenicol Nitrofuran metabolites Phenolics Veterinary drug residues
Cyanotoxins Nitroimidazoles Phenoxy acid herbicides Water soluble vitamins
Dexamethasone and
Betamethasone
Nitrosamines Phthalates
Waters LC 204 multi residue
pesticides standards kit
ยฉ2016 Waters Corporation 20
Sample Analysis in QuanPedia
Step 1 : Run samples Step 2 : Select an analysis
MS method
LC
method
TargetLynx
method
Step 3: Select methods to be generatedStep 4: Input your sample details
ยฉ2016 Waters Corporation 21
Automated Quan Workflow:
QuanPedia
QuanPedia
ยฉ2016 Waters Corporation 22
Expanding the Scope of QuanPedia
Import New Compounds
Excel spreadsheet
Notepad or Word
Optimised Compounds
PICS
ยฉ2016 Waters Corporation 23
PIC Scan
Acquisition
MRM
Acquisition
Product Ion Confirmation (PIC) Scan:
Rapid Switching Provides Increased Confidence
Post Apex
PIC SCAN
ยฉ2016 Waters Corporation 24
Overlay UPLC-MS/MS Chromatogram
Grapes Post-Spiked at 10 ppb
ยฉ2016 Waters Corporation 25
Selected MRM Chromatograms
at 10ppb (MRL)
ยฉ2016 Waters Corporation 26
Automated Quan Workflow:
TargetLynx XS Data Processing and Review
ยฉ2016 Waters Corporation 27
Linearity by UPLC-MS/MS
in Green Grape Matrix
Compound Range R2
Acetamiprid 1 ppb to 100 ppb 0.998
Aldicarb 1 ppb to 500 ppb 0.996
Aldicarb sulfone 1 ppb to 500 ppb 0.997
Ametryn 1 ppb to 500 ppb 0.994
Aminocarb 1 ppb to 500 ppb 0.999
Azoxystrobin 1 ppb to 500 ppb 0.993
Benalaxyl 1 ppb to 500 ppb 0.998
Bendiocarb 1 ppb to 500 ppb 0.999
Benzoximate 1 ppb to 500 ppb 0.998
Bitertanol 1 ppb to 500 ppb 0.998
Buprofezine 1 ppb to 500 ppb 0.998
Butoxycarboxim 1 ppb to 500 ppb 0.997
Carbendazim 1 ppb to 500 ppb 0.995
Carbetamide 1 ppb to 500 ppb 0.997
Carbofuran 1 ppb to 500 ppb 0.999
Carbofuran 3-hydroxy 1 ppb to 500 ppb 0.998
Chlortoluron 1 ppb to 500 ppb 0.999
Clofentezine 1 ppb to 500 ppb 0.998
Desmedipham 1 ppb to 500 ppb 0.999
Dimoxystrobin 1 ppb to 500 ppb 0.997
Diuron 1 ppb to 500 ppb 0.994
Ethiofencarb 1 ppb to 500 ppb 0.999
Ethofumesate 1 ppb to 500 ppb 0.998
Fenamidone 1 ppb to 500 ppb 0.998
Fenbuconazole 1 ppb to 500 ppb 0.997
Fenobucarb 1 ppb to 500 ppb 0.996
Compound Range R2
Fenoxycarb 1 ppb to 500 ppb 0.996
Fenpyroximate 1 ppb to 500 ppb 0.997
Fenuron 1 ppb to 500 ppb 0.999
Hexaconazole 1 ppb to 500 ppb 0.998
Imidacloprid 1 ppb to 500 ppb 0.996
Isoprocarb 1 ppb to 500 ppb 0.995
Isoproturon 1 ppb to 500 ppb 0.999
Linuron 1 ppb to 500 ppb 0.997
Mandipropamid 1 ppb to 500 ppb 0.998
Mefenacet 1 ppb to 500 ppb 0.999
Mepronil 1 ppb to 500 ppb 0.994
Metalaxyl 1 ppb to 500 ppb 0.997
Oxamyl 1 ppb to 500 ppb 0.997
Phenmedipham 1 ppb to 500 ppb 0.999
Picoxystrobin 1 ppb to 500 ppb 0.994
Piperonyl butoxide 1 ppb to 500 ppb 0.998
Pirimicarb 1 ppb to 500 ppb 0.997
Promecarb 1 ppb to 500 ppb 0.995
Prometryn 1 ppb to 500 ppb 0.998
Propargite 1 ppb to 500 ppb 0.996
Propoxur 1 ppb to 500 ppb 0.997
Pyracarbolid 1 ppb to 500 ppb 0.999
Simetryn 1 ppb to 500 ppb 0.999
Spirotetramat 1 ppb to 500 ppb 0.997
Tebuconazole 1 ppb to 500 ppb 0.997
Tebuthiuron 1 ppb to 500 ppb 0.998
ยฉ2016 Waters Corporation 28
Recovery by UPLC-MS/MS
in Green Grape Matrix
Name Average (n=3) %RSD
Acetamiprid 99.3 4.8
Aldicarb 98.9 6.8
Aldicarb sulfone 99.2 5.8
Ametryn 100.8 5.3
Aminocarb 90.8 5.2
Azoxystrobin 101.0 6.0
Benalaxyl 103.9 4.8
Bendiocarb 103.3 5.8
Benzoximate 99.4 6.9
Bitertanol 97.6 9.1
Bupirimate 107.7 9.6
Buprofezin 102.0 7.1
Butafenacil 107.8 8.1
Butocarboxim 98.0 6.5
Butoxycarboxim 98.2 6.0
Carbaryl 96.8 4.4
Carbendazim 97.8 6.0
Carbetamide 97.7 5.6
Carbofuran 102.4 5.4
Carbofuran-3-hydroxy 103.7 6.4
Carboxin 99.5 5.3
Carfentrazone-ethyl 109.8 16.6
Chlorantraniliprole 89.2 14.0
ยฉ2016 Waters Corporation 29
Incurred Residues by UPLC-MS/MS
Green Grapes
Name
Retention
Time
Match
Ion Ratio
Match
Incurred
Residue
(mg/kg)
EU MRLs
(mg/kg)
Boscalid 0.006 5
Buprofezin 0.001 1
Fenhexamid 0.036 15
Imidacloprid 0.012 1
Methoxyfenozide 0.018 1
Pyraclostrobin 0.001 1
Trifloxystrobin 0.001 3
Incurred residues detected are well below the EU MRLs
ยฉ2016 Waters Corporation 30
Automated Quan Workflow:
QC Monitor
Run samples
Decision time
๏‚ง Reinject
๏‚ง Troubleshoot
Criteria defined by the
requirements of your
lab and method
ยฉ2016 Waters Corporation 31
TrendPlot - Monitoring Long-Term
Robustness
๏‚ก Long term system
monitoring
๏‚ก Essential record
for auditors
๏‚ก Tool for effective
lab management
ยฉ2016 Waters Corporation 32
Multi-Residue Pesticides Analysis in Green Grapes
Using APGC-MS/MS
ยฉ2016 Waters Corporation 33
๏‚ก Ion Source Versatility
โ€“ Universal source architecture: Enables the widest range of ionisation
techniques to be utilised
โ€“ Simple and quick: Allowing you to change between ion source options in
minutes
Universal Source Options:
UPLC to APGC
ยฉ2016 Waters Corporation 34
๏‚ก APGC is an inlet option of the XEVO universal source, readily
interchangeable with UPLC, etc.
๏‚ก Operates
โ€“ At atmospheric pressure, thus allowing higher gas flows to be applied
โ€“ By APCI like ionisation using a corona discharge pin, thus allowing ionisation
by proton and charge transfer
Atmospheric Pressure Gas Chromatography
ยฉ2016 Waters Corporation 35
APGC Video
ยฉ2016 Waters Corporation 36
Ionisation Comparison: APGC vs EI
Standrad D 2PPM Split 10:1 DRE H2O
m/z
25 50 75 100 125 150 175 200 225 250 275
%
0
100
jv250809test005 533 (9.336) Cm (531:534-518:526) TOF MS AP+
3.50e4230.0066198.9643
170.9724
124.9845
93.0114
232.0065
APGC - Proton Transfer
C5H12NO3PS2
M+ยท 229
Classic EI
Mix C 1 ppm
m/z
60 80 100 120 140 160 180 200 220 240
%
0
100
API033 533 (10.107) Cm (527:533-465:517) TOF MS EI+
5.46e487.0137
58.0303
63.0009
93.0101
124.9828
93.0561
104.0112
201.0790
186.0549173.0479
158.0325142.9955 203.0784
229.0006
Dimethoate
ยฉ2016 Waters Corporation 37
GC-MS Conditions
GC System: Agilent 7890
Column: DB-5 30m x 0.25 mm x 0.25 ยตm
Injection Mode: Splitless
Inlet Liner: Single gooseneck SKY deactivated
Injector Temp: 280 ยฐC
Flow Rate: 2.0 mL/min
Injection volume: 1.0 ยตL
Transfer Line Temp: 320 ยฐC
Carrier Gas: Helium
Oven Program:
Ramp (ยฐC/min) Temp (ยฐC) Hold (min)
35 1.2
25 320 2
MS system: Xevo TQ-S micro
Corona: 5.0 uA
Source Temp: 150ยฐC
Auxiliary Flow: 250 L/hr
Cone Gas Flow: 50 L/hr
ยฉ2016 Waters Corporation 38
Overlay APGC-MS/MS Chromatogram
Grapes post-spiked at 10 ppb
ยฉ2016 Waters Corporation 39
Example MRM chromatograms
at 10ppb (MRL)
ยฉ2016 Waters Corporation 40
Linearity by APGC-MS/MS
in Green Grape Matrix
Compound Range R2
Malathion 0.25 ppb to 50 ppb 0.998
Chlozolinate 0.5 ppb to 50 ppb 0.998
Pirimiphos-ethyl 0.25 ppb to 50 ppb 0.999
Prochloraz 0.25 ppb to 100 ppb 0.999
Carfentrazone ethyl 0.25 ppb to 100 ppb 0.999
Biphenyl 0.1 ppb to 100 ppb 0.999
Terbacil 1.0 ppb to 100 ppb 0.999
Diclobenil 0.25 ppb to 100 ppb 0.999
Chlorpropham 1.0 ppb to 50 ppb 0.999
Tefluthrin 0.5 ppb to 50 ppb 0.999
Anthraquinone 0.5 ppb to 100 ppb 0.999
Propachlor 0.5 ppb to 100 ppb 0.999
Terbutylazine 0.5 ppb to 50 ppb 0.999
Clomazone 0.5 ppb to 50 ppb 0.999
Etridazole 0.5 ppb to 100 ppb 0.998
Linuron 0.5 ppb to 50 ppb 0.999
Hexazinone 0.25 ppb to 50 ppb 0.999
Phorate 1.0 ppb to 50 ppb 0.998
Fenson 0.25 ppb to 100 ppb 0.999
Diallate 0.25 ppb to 50 ppb 0.999
Fenitrothion 0.5 ppb to 50 ppb 0.998
Fenthion 0.5 ppb to 100 ppb 0.999
4,4'-Methoxychlor Olefin 0.5 ppb to 50 ppb 0.996
Sulfotep 0.5 ppb to 100 ppb 0.996
Fenchlorphos 0.5 ppb to 50 ppb 0.995
Sulprofos 0.25 ppb to 50 ppb 0.996
Flutolanil 0.5 ppb to 50 ppb 0.995
Compound Range R2
Pyridaphenthion 0.5 ppb to 100 ppb 0.997
Phenothrin 0.5 ppb to 50 ppb 0.995
Phosalone 0.1 ppb to 50 ppb 0.999
Transfluthrin 0.25 ppb to 100 ppb 0.997
Fluazifop-p-butyl 0.1 ppb to 50 ppb 0.999
Ethion 0.25 ppb to 50 ppb 0.998
Flucythrinate 1 0.5 ppb to 100 ppb 0.999
Flucythrinate 2 0.5 ppb to 50 ppb 0.996
Deltamethrin 0.25 ppb to 50 ppb 0.998
Tetrahydrophthalimide 0.5 ppb to 100 ppb 0.998
2-Phenylphenol 1.0 ppb to 100 ppb 0.999
Bifenthrin 0.5 ppb to 50 ppb 0.997
Mevinphos 0.25 ppb to 100 ppb 0.993
Pebulate 0.25 ppb to 50 ppb 0.991
Cycloate 1.0 ppb to 50 ppb 0.998
Atrazine 0.5 ppb to 100 ppb 0.994
Propanil 0.5 ppb to 50 ppb 0.996
2,3,5,6-Tetrachloroaniline 1.0 ppb to 100 ppb 0.997
o,p'-DDD 0.25 ppb to 50 ppb 0.996
Diphenamid 0.25 ppb to 50 ppb 0.996
Propyzamide 0.5 ppb to 50 ppb 0.996
Dimethachlor 0.25 ppb to 100 ppb 0.992
Methyl parathion 0.1 ppb to 50 ppb 0.999
Paclobutrazol 1.0 ppb to 100 ppb 0.997
Bioallethrin 1.0 ppb to 100 ppb 0.996
ยฉ2016 Waters Corporation 41
Incurred Residues by APGC-MS/MS
Green Grapes
Name
Retention
Time
Match
Ion Ratio
Match
Incurred
Residue
(mg/kg)
EU MRLs
(mg/kg)
Pyriproxyfen 0.0009 0.05
Tetrahydrophthalimide 0.0003 0.02
2-Phenylphenol 0.0007 0.05
Pyrimethanil 0.008 5
Anthraquinone 0.0004 0.01
Incurred residues detected are well below the EU MRLs
ยฉ2016 Waters Corporation 42
Analysis of 460 Pesticides in 10 different Food
Commodities by APGC-MS/MS
Collaboration with NOFA Lab, Netherlands
ยฉ2016 Waters Corporation 43
๏‚ก Commodity independent
โ€“ Semi quantitative screening
โ€“ 10 commodities screened against solvent curve
๏‚ก 460 pesticides (92.4 %) passed validation criteria
๏ % Recovery of between 70 and 120 %
๏ % rRSD < 20 %
๏ LoD < 5 ยตg/kg
๏‚ก 32 pesticides (7.6%) failed due to poor analyte recovery
(<70%)
โ€“ Including nitro- and chloro- phenols, captan and folpet
courtesy of NofaLab, the Netherlands, 2015
NOFA Lab โ€“ Analysis of 460 Pesticides
in 10 different Food Commodities
ยฉ2016 Waters Corporation 44
Method results
courtesy of NofaLab, the Netherlands, 2015
ยฉ2016 Waters Corporation 45
APGC vs EI: Benefits
APGC EI Customer benefit
Injection of sample in
mg
0.1- 0.5 mg 5- 50 mg (LOD still higher)
Inject less, chromatography
longer stable
Retention times
Neglect able shifts (small
scan windows)
Large shifts (large scan
windows)
More confidence, less
reprocess, save time
Response Stable
Large variation and sudden
drop
Less maintenance
Cleaning the source
Once or twice a year
(preventive)
Once a week (when
needed)
No need to vent the system,
clean the source, change the
filament
Replacing the front
column/liner (inject
less)
Every two weeks
(preventive)
Once or twice a week
(when needed)
Less downtime
Replacing the analytical
column (inject less)
3 to 6 months (when
needed)
Once a month (when
needed)
Less downtime, save
consumable
Downtime
A week per year (most
preventive)
One or two months per
year (most trouble
shooting)
Positive ROI
Inject Less
Clean Less
Replace Less
Down Less
courtesy of NofaLab, the Netherlands
ยฉ2016 Waters Corporation 46
๏‚ก Improved efficiencies for LC and GC amenable multi-residue pesticides
analysis on a single instrument platform
๏‚ง Innovative workflow strategies for MS quantification and to maximize
laboratory efficiency
APGC-
MS/MS
UPLC-
MS/MS
Summary
โˆ’ IntelliStart
โˆ’ QuanPedia
โˆ’ TargetLynx XS
โˆ’ TrendPlot
โˆ’ RADAR
โˆ’ PICs
ยฉ2016 Waters Corporation 47
Multi-Residue Pesticide Analysis in
Food Matrices โ€“ Other Applications
Resources:
โ€ข LC- and GC- MS/MS pesticides in tea: 720004819en
โ€ข LC- MS/MS pesticides in chilli powder: 720005285en
โ€ข LC-MS/MS pesticides in okra: 720004789en
โ€ข LC- MS/MS pesticides in chilli powder: 720005559en
โ€ข GC- MS/MS pesticides in fruits and vegetables: 720004952en
โ€ข LC- and GC- MS/MS pesticides in botanicals: 720005659en
โ€ขLC- and GC- MS/MS pesticides in ginseng: 720005006en
โ€ข Dilute and shoot pesticides in fruit juices: 720004403en
โ€ข Food Testing Application Notebook: 720002565en
ยฉ2016 Waters Corporation 48
www.waters.com
Thank you for your attention
Any questions

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Routine Quantification of Pesticides in Food Matrices using UPLC APGC-MSMS - Waters Corporation Food Safety

  • 1. ยฉ2016 Waters Corporation 1 Routine Quantification of Multi-Residue Pesticides in Food Matrices using UPLC and APGC coupled to MS/MS
  • 2. ยฉ2016 Waters Corporation 2 Overview ๏‚ก Challenges and method requirements for multi-residue analysis ๏‚ก Single instrument platform for LC and GC amenable pesticides ๏‚ก Sample preparation and analysis workflow ๏‚ก Acquisition modes โ€“ MS/MS, RADAR, PICS ๏‚ก Quanpedia database - Pesticides, metabolites, toxins and other contaminants ๏‚ก Collaboration (Nofa Lab) - Validation study for analysis of 460 pesticides in 10 different food commodities using APGC-MS/MS ๏‚ก Summary and Conclusions
  • 3. ยฉ2016 Waters Corporation 3 Challenges in Multi Residue Pesticide Analysis of Food Products Changing Legislation Demanding Performance Multitude of Food Types Variety of Pesticides
  • 4. ยฉ2016 Waters Corporation 4 ๏‚ก High throughput: Generic QuEChERS clean up ๏‚ก Quantification & confirmation: gold standard MS/MS ๏‚ก Sensitivity: 0.01 mg/kg ๏‚ก Method robustness: System up time, instrument maintenance Multi Residue Pesticides in Food Method Requirements Food product Representative extract GC with MS/MS detection LC with MS/MS detection
  • 5. ยฉ2016 Waters Corporation 5 Xevo TQD Xevo TQ-S XEVO Tandem Quadrupole Systems Xevo TQ-S micro ๏‚ก Routine UPLC-MS/MS ๏‚ก RADAR acquisition mode ๏‚ก Universal ion source ๏‚ก Compact with high sensitivity ๏‚ก RADAR acquisition mode ๏‚ก Universal ion source ๏‚ก Fast data acquisition ๏‚ก Xtended Dynamic Range ๏‚ก Ultimate sensitivity ๏‚ก RADAR acquisition mode ๏‚ก Universal ion source ๏‚ก ScanWave Enhanced product ion scanning Ultimate sensitivity and reliability Sensitive, reliable and compact Robust, reliable and proven
  • 6. ยฉ2016 Waters Corporation 6 Extended Dynamic Range ๏‚ก Provides up to 6 orders of linear dynamic range ๏‚ก Easier to transfer methods from other instruments with higher or lower sensitivities ๏‚ก Accessible sensitivity 0.80 0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 % 0 1x, 1 ng 1x, 100 pg 10x, 10 pg 82x, 1pg 876x, 100 fg 10,000x, 10 fg 10,000x magnification, 1 fg
  • 7. ยฉ2016 Waters Corporation 7 Increased Capability LC and GC Workflow on one MS Platform UPLC-MS/MS APGC-MS/MS Quantitative & Confirmatory Analysis LC and GC with XEVO TQ-S micro
  • 8. ยฉ2016 Waters Corporation 8 Quantitative & Confirmatory Analysis LC and GC with XEVO TQ-S micro 10 ยตg/kg Compound name: Pyracarbolid Correlation coefficient: r = 0.999741, r^2 = 0.999482 Calibration curve: 2921.65 * x + -539.66 Response type: External Std, Area Curve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None Standard Addition Concentration : -0.184711 ppb -0 10 20 30 40 50 60 70 80 90 100 Response -0 100000 200000 ppb Residual -2.00 0.00 2.00 Compound name: Pyracarbolid Correlation coefficient: r = 0.999741, r^2 = 0.999482 Calibration curve: 2921.65 * x + -539.66 Response type: External Std, Area Curve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None ppb -0 10 20 30 40 50 60 70 80 90 100 Response -0 100000 200000 ppb Residual -2.00 0.00 2.00
  • 9. ยฉ2016 Waters Corporation 9 Generic Cleanup with QuEChERS Homogenisation 15 g sample DisQuE extraction 15 mL 1 % acetic acid in ACN Centrifuge 3500 RPM 5 min DisQuE Tube 2 186004832 Dilute 1 in 10 in water Solvent Exchange 500 ยตL ethyl acetate APGCUPLC
  • 10. ยฉ2016 Waters Corporation 10 UPLC-MS/MS ๏‚ง Diluted QuEChERS extract, spiked with LC pesticide mix ๏‚ง LC multi-residue pesticide mix ~204 compounds ๏‚ง Solvent curve - 1 to 500 ppb ๏‚ง Matrix match spiked curve - 1 to 500 ppb LC - 204 pesticides mix Experiments APGC-MS/MS ๏‚ง After solvent exchange of QuEChERS extract, spiked with GC pesticide mix ๏‚ง GC multi-residue pesticide mix ~203 compounds ๏‚ง Solvent curve โ€“ 0.1 to 100 ppb ๏‚ง Matrix match spiked curve โ€“ 0.1 to 100 ppb ๏‚ง Accurately detect and quantify multi-residue pesticides in a wide range of fruits, vegetables, and other commodities by UPLC-MS/MS ๏‚ง Full kit contains 204 pesticides, formulated and grouped for maximum long-term stability ๏‚ง Optimized multi-residue pesticide method with UPLC conditions and MS/MS transitions available
  • 11. ยฉ2016 Waters Corporation 11 Determine Sample Prep Efficiency ๏‚ก What is RADAR? โ€“ Rapid electronics allow instrument to switch between MRM & full scan โ€“ Added information can be gained from full scan data in routine analyses โ€ข Intelligent decision making โ€ข Improves method development โ€ข Monitor matrix components โ€ข Detect un-targeted adulterants ๏‚ก How do I set it up on the instrument? - Parallel MRM with full scan data acquisition
  • 12. ยฉ2016 Waters Corporation 12 Grape Avocado Marjoram Ginger Ultra Trace Analysis: Sample Complexity Xevo TQ-S
  • 13. ยฉ2016 Waters Corporation 13 Ultra trace analysis: Matrix effects DisQuE Ginger QC extract pesticides @ 0.01 mg/kg (10 ppb) Cyromazine Simetryn Atrazine Azinphos -ethyl Poor peak shape Low calculated recoveries High Matrix background Xevo TQ-S
  • 14. ยฉ2016 Waters Corporation 14 Ultra trace analysis: Reduced matrix effects (10x Dilution) Cyromazine Simetryn Atrazine Azinphos -ethyl 10 x dilution of Ginger extract All peaks detected, recoveries good Reduced Matrix background by 10X dilution Improved peak shape -54% -58% -47% Reduced ion suppression
  • 15. ยฉ2016 Waters Corporation 15 Multi-Residue Pesticide Analysis in Green Grapes Using UPLC-MS/MS
  • 16. ยฉ2016 Waters Corporation 16 UPLC-MS Conditions LC System: Waters ACQUITY H-Class Column: ACQUITY UPLC BEH C18 2.1 x 100 mm, 1.7 ยตm Column Temp: 45 หšC Flow Rate: 0.450 mL/min Injection volume: 10 ยตL Mobile Phase A: 10mL of 1M ammonium acetate (pH5.0) + 990mL Water Mobile Phase B: 10mL of 1M ammonium acetate (pH 5.0) + 990mL MeOH Gradient: Min %A %B Curve Initial 98.0 2.0 0.25 98.0 2.0 6 12.25 1.0 99.0 6 13.00 1.0 99.0 6 13.01 98.0 2.0 6 17.00 98.0 2.0 6 MS System: Xevo TQ-S micro Capillary (kV): 1.0 Source Temp.: 150ยฐC Desolvation Temp.: 500ยฐC Desolvation Gas Flow: 1000 L/Hr MRM Transitions: TQ-S micro Quanpedia
  • 17. ยฉ2016 Waters Corporation 17 โ€ข Is my system ready, does it satisfy lab quality requirements? Set-up and check analytical system Automated Quan Workflow: From System Setup to Data Processing โ€ข The QuanPediaโ„ข database allows for efficient method management Select or create LC-MS/MS method โ€ข TargetLynx XS streamlines automated quantitative data review and reporting Comprehensive data processing and review โ€ข Trending inter- and intra-batch QC and sample results over time is easy with TrendPlot Compare data day to day, week to week โ€ข Automated real-time QC checking with QCMonitor prevents wasting valuable samples Critical QC Information Delivered Real Time
  • 18. ยฉ2016 Waters Corporation 18 IntelliStart: Ready to Use System ๏‚ก IntelliStart ๏‚ก In-built Fluidics ๏‚ก Automated delivery of reference solutions ๏‚ก Automated flow switching
  • 19. ยฉ2016 Waters Corporation 19 Quanpedia for XEVO TQ-S micro ๏‚ก Compound database includes โ€“ LC-MS/MS method files (UPLC and MRM conditions) โ€“ TargetLynx quantification โ€“ PICS โ€“ Options for modifying and optimizing methods ๏‚ก Analyses include: Alternaria toxins Diquat and Paraquat Patulin Polyphenols Aminoglycosides Endocrine disrupting compounds Perfluorinated Progestogens Amphetamines Glyphosate and AMPA Pesticide polarity switching Quinolones Androgens and progestogens Heterocyclic amines Pesticide screening Sudan dyes 1 Anthelminitics Hormones Pesticides (APEDA- India) Sulfonamides Antibiotics Japanese positive list Pesticides 375 Tetracyclines Avermectins Marine biotoxins Pesticides in baby food Thyreostats Beta agonists Melamine Pharmaceutical and personal care products Triarylmethane dyes Bisphenol Mycotoxins Pharmaceuticals Triarylmethane dyes and metabolites Chloramphenicol Nitrofuran metabolites Phenolics Veterinary drug residues Cyanotoxins Nitroimidazoles Phenoxy acid herbicides Water soluble vitamins Dexamethasone and Betamethasone Nitrosamines Phthalates Waters LC 204 multi residue pesticides standards kit
  • 20. ยฉ2016 Waters Corporation 20 Sample Analysis in QuanPedia Step 1 : Run samples Step 2 : Select an analysis MS method LC method TargetLynx method Step 3: Select methods to be generatedStep 4: Input your sample details
  • 21. ยฉ2016 Waters Corporation 21 Automated Quan Workflow: QuanPedia QuanPedia
  • 22. ยฉ2016 Waters Corporation 22 Expanding the Scope of QuanPedia Import New Compounds Excel spreadsheet Notepad or Word Optimised Compounds PICS
  • 23. ยฉ2016 Waters Corporation 23 PIC Scan Acquisition MRM Acquisition Product Ion Confirmation (PIC) Scan: Rapid Switching Provides Increased Confidence Post Apex PIC SCAN
  • 24. ยฉ2016 Waters Corporation 24 Overlay UPLC-MS/MS Chromatogram Grapes Post-Spiked at 10 ppb
  • 25. ยฉ2016 Waters Corporation 25 Selected MRM Chromatograms at 10ppb (MRL)
  • 26. ยฉ2016 Waters Corporation 26 Automated Quan Workflow: TargetLynx XS Data Processing and Review
  • 27. ยฉ2016 Waters Corporation 27 Linearity by UPLC-MS/MS in Green Grape Matrix Compound Range R2 Acetamiprid 1 ppb to 100 ppb 0.998 Aldicarb 1 ppb to 500 ppb 0.996 Aldicarb sulfone 1 ppb to 500 ppb 0.997 Ametryn 1 ppb to 500 ppb 0.994 Aminocarb 1 ppb to 500 ppb 0.999 Azoxystrobin 1 ppb to 500 ppb 0.993 Benalaxyl 1 ppb to 500 ppb 0.998 Bendiocarb 1 ppb to 500 ppb 0.999 Benzoximate 1 ppb to 500 ppb 0.998 Bitertanol 1 ppb to 500 ppb 0.998 Buprofezine 1 ppb to 500 ppb 0.998 Butoxycarboxim 1 ppb to 500 ppb 0.997 Carbendazim 1 ppb to 500 ppb 0.995 Carbetamide 1 ppb to 500 ppb 0.997 Carbofuran 1 ppb to 500 ppb 0.999 Carbofuran 3-hydroxy 1 ppb to 500 ppb 0.998 Chlortoluron 1 ppb to 500 ppb 0.999 Clofentezine 1 ppb to 500 ppb 0.998 Desmedipham 1 ppb to 500 ppb 0.999 Dimoxystrobin 1 ppb to 500 ppb 0.997 Diuron 1 ppb to 500 ppb 0.994 Ethiofencarb 1 ppb to 500 ppb 0.999 Ethofumesate 1 ppb to 500 ppb 0.998 Fenamidone 1 ppb to 500 ppb 0.998 Fenbuconazole 1 ppb to 500 ppb 0.997 Fenobucarb 1 ppb to 500 ppb 0.996 Compound Range R2 Fenoxycarb 1 ppb to 500 ppb 0.996 Fenpyroximate 1 ppb to 500 ppb 0.997 Fenuron 1 ppb to 500 ppb 0.999 Hexaconazole 1 ppb to 500 ppb 0.998 Imidacloprid 1 ppb to 500 ppb 0.996 Isoprocarb 1 ppb to 500 ppb 0.995 Isoproturon 1 ppb to 500 ppb 0.999 Linuron 1 ppb to 500 ppb 0.997 Mandipropamid 1 ppb to 500 ppb 0.998 Mefenacet 1 ppb to 500 ppb 0.999 Mepronil 1 ppb to 500 ppb 0.994 Metalaxyl 1 ppb to 500 ppb 0.997 Oxamyl 1 ppb to 500 ppb 0.997 Phenmedipham 1 ppb to 500 ppb 0.999 Picoxystrobin 1 ppb to 500 ppb 0.994 Piperonyl butoxide 1 ppb to 500 ppb 0.998 Pirimicarb 1 ppb to 500 ppb 0.997 Promecarb 1 ppb to 500 ppb 0.995 Prometryn 1 ppb to 500 ppb 0.998 Propargite 1 ppb to 500 ppb 0.996 Propoxur 1 ppb to 500 ppb 0.997 Pyracarbolid 1 ppb to 500 ppb 0.999 Simetryn 1 ppb to 500 ppb 0.999 Spirotetramat 1 ppb to 500 ppb 0.997 Tebuconazole 1 ppb to 500 ppb 0.997 Tebuthiuron 1 ppb to 500 ppb 0.998
  • 28. ยฉ2016 Waters Corporation 28 Recovery by UPLC-MS/MS in Green Grape Matrix Name Average (n=3) %RSD Acetamiprid 99.3 4.8 Aldicarb 98.9 6.8 Aldicarb sulfone 99.2 5.8 Ametryn 100.8 5.3 Aminocarb 90.8 5.2 Azoxystrobin 101.0 6.0 Benalaxyl 103.9 4.8 Bendiocarb 103.3 5.8 Benzoximate 99.4 6.9 Bitertanol 97.6 9.1 Bupirimate 107.7 9.6 Buprofezin 102.0 7.1 Butafenacil 107.8 8.1 Butocarboxim 98.0 6.5 Butoxycarboxim 98.2 6.0 Carbaryl 96.8 4.4 Carbendazim 97.8 6.0 Carbetamide 97.7 5.6 Carbofuran 102.4 5.4 Carbofuran-3-hydroxy 103.7 6.4 Carboxin 99.5 5.3 Carfentrazone-ethyl 109.8 16.6 Chlorantraniliprole 89.2 14.0
  • 29. ยฉ2016 Waters Corporation 29 Incurred Residues by UPLC-MS/MS Green Grapes Name Retention Time Match Ion Ratio Match Incurred Residue (mg/kg) EU MRLs (mg/kg) Boscalid 0.006 5 Buprofezin 0.001 1 Fenhexamid 0.036 15 Imidacloprid 0.012 1 Methoxyfenozide 0.018 1 Pyraclostrobin 0.001 1 Trifloxystrobin 0.001 3 Incurred residues detected are well below the EU MRLs
  • 30. ยฉ2016 Waters Corporation 30 Automated Quan Workflow: QC Monitor Run samples Decision time ๏‚ง Reinject ๏‚ง Troubleshoot Criteria defined by the requirements of your lab and method
  • 31. ยฉ2016 Waters Corporation 31 TrendPlot - Monitoring Long-Term Robustness ๏‚ก Long term system monitoring ๏‚ก Essential record for auditors ๏‚ก Tool for effective lab management
  • 32. ยฉ2016 Waters Corporation 32 Multi-Residue Pesticides Analysis in Green Grapes Using APGC-MS/MS
  • 33. ยฉ2016 Waters Corporation 33 ๏‚ก Ion Source Versatility โ€“ Universal source architecture: Enables the widest range of ionisation techniques to be utilised โ€“ Simple and quick: Allowing you to change between ion source options in minutes Universal Source Options: UPLC to APGC
  • 34. ยฉ2016 Waters Corporation 34 ๏‚ก APGC is an inlet option of the XEVO universal source, readily interchangeable with UPLC, etc. ๏‚ก Operates โ€“ At atmospheric pressure, thus allowing higher gas flows to be applied โ€“ By APCI like ionisation using a corona discharge pin, thus allowing ionisation by proton and charge transfer Atmospheric Pressure Gas Chromatography
  • 36. ยฉ2016 Waters Corporation 36 Ionisation Comparison: APGC vs EI Standrad D 2PPM Split 10:1 DRE H2O m/z 25 50 75 100 125 150 175 200 225 250 275 % 0 100 jv250809test005 533 (9.336) Cm (531:534-518:526) TOF MS AP+ 3.50e4230.0066198.9643 170.9724 124.9845 93.0114 232.0065 APGC - Proton Transfer C5H12NO3PS2 M+ยท 229 Classic EI Mix C 1 ppm m/z 60 80 100 120 140 160 180 200 220 240 % 0 100 API033 533 (10.107) Cm (527:533-465:517) TOF MS EI+ 5.46e487.0137 58.0303 63.0009 93.0101 124.9828 93.0561 104.0112 201.0790 186.0549173.0479 158.0325142.9955 203.0784 229.0006 Dimethoate
  • 37. ยฉ2016 Waters Corporation 37 GC-MS Conditions GC System: Agilent 7890 Column: DB-5 30m x 0.25 mm x 0.25 ยตm Injection Mode: Splitless Inlet Liner: Single gooseneck SKY deactivated Injector Temp: 280 ยฐC Flow Rate: 2.0 mL/min Injection volume: 1.0 ยตL Transfer Line Temp: 320 ยฐC Carrier Gas: Helium Oven Program: Ramp (ยฐC/min) Temp (ยฐC) Hold (min) 35 1.2 25 320 2 MS system: Xevo TQ-S micro Corona: 5.0 uA Source Temp: 150ยฐC Auxiliary Flow: 250 L/hr Cone Gas Flow: 50 L/hr
  • 38. ยฉ2016 Waters Corporation 38 Overlay APGC-MS/MS Chromatogram Grapes post-spiked at 10 ppb
  • 39. ยฉ2016 Waters Corporation 39 Example MRM chromatograms at 10ppb (MRL)
  • 40. ยฉ2016 Waters Corporation 40 Linearity by APGC-MS/MS in Green Grape Matrix Compound Range R2 Malathion 0.25 ppb to 50 ppb 0.998 Chlozolinate 0.5 ppb to 50 ppb 0.998 Pirimiphos-ethyl 0.25 ppb to 50 ppb 0.999 Prochloraz 0.25 ppb to 100 ppb 0.999 Carfentrazone ethyl 0.25 ppb to 100 ppb 0.999 Biphenyl 0.1 ppb to 100 ppb 0.999 Terbacil 1.0 ppb to 100 ppb 0.999 Diclobenil 0.25 ppb to 100 ppb 0.999 Chlorpropham 1.0 ppb to 50 ppb 0.999 Tefluthrin 0.5 ppb to 50 ppb 0.999 Anthraquinone 0.5 ppb to 100 ppb 0.999 Propachlor 0.5 ppb to 100 ppb 0.999 Terbutylazine 0.5 ppb to 50 ppb 0.999 Clomazone 0.5 ppb to 50 ppb 0.999 Etridazole 0.5 ppb to 100 ppb 0.998 Linuron 0.5 ppb to 50 ppb 0.999 Hexazinone 0.25 ppb to 50 ppb 0.999 Phorate 1.0 ppb to 50 ppb 0.998 Fenson 0.25 ppb to 100 ppb 0.999 Diallate 0.25 ppb to 50 ppb 0.999 Fenitrothion 0.5 ppb to 50 ppb 0.998 Fenthion 0.5 ppb to 100 ppb 0.999 4,4'-Methoxychlor Olefin 0.5 ppb to 50 ppb 0.996 Sulfotep 0.5 ppb to 100 ppb 0.996 Fenchlorphos 0.5 ppb to 50 ppb 0.995 Sulprofos 0.25 ppb to 50 ppb 0.996 Flutolanil 0.5 ppb to 50 ppb 0.995 Compound Range R2 Pyridaphenthion 0.5 ppb to 100 ppb 0.997 Phenothrin 0.5 ppb to 50 ppb 0.995 Phosalone 0.1 ppb to 50 ppb 0.999 Transfluthrin 0.25 ppb to 100 ppb 0.997 Fluazifop-p-butyl 0.1 ppb to 50 ppb 0.999 Ethion 0.25 ppb to 50 ppb 0.998 Flucythrinate 1 0.5 ppb to 100 ppb 0.999 Flucythrinate 2 0.5 ppb to 50 ppb 0.996 Deltamethrin 0.25 ppb to 50 ppb 0.998 Tetrahydrophthalimide 0.5 ppb to 100 ppb 0.998 2-Phenylphenol 1.0 ppb to 100 ppb 0.999 Bifenthrin 0.5 ppb to 50 ppb 0.997 Mevinphos 0.25 ppb to 100 ppb 0.993 Pebulate 0.25 ppb to 50 ppb 0.991 Cycloate 1.0 ppb to 50 ppb 0.998 Atrazine 0.5 ppb to 100 ppb 0.994 Propanil 0.5 ppb to 50 ppb 0.996 2,3,5,6-Tetrachloroaniline 1.0 ppb to 100 ppb 0.997 o,p'-DDD 0.25 ppb to 50 ppb 0.996 Diphenamid 0.25 ppb to 50 ppb 0.996 Propyzamide 0.5 ppb to 50 ppb 0.996 Dimethachlor 0.25 ppb to 100 ppb 0.992 Methyl parathion 0.1 ppb to 50 ppb 0.999 Paclobutrazol 1.0 ppb to 100 ppb 0.997 Bioallethrin 1.0 ppb to 100 ppb 0.996
  • 41. ยฉ2016 Waters Corporation 41 Incurred Residues by APGC-MS/MS Green Grapes Name Retention Time Match Ion Ratio Match Incurred Residue (mg/kg) EU MRLs (mg/kg) Pyriproxyfen 0.0009 0.05 Tetrahydrophthalimide 0.0003 0.02 2-Phenylphenol 0.0007 0.05 Pyrimethanil 0.008 5 Anthraquinone 0.0004 0.01 Incurred residues detected are well below the EU MRLs
  • 42. ยฉ2016 Waters Corporation 42 Analysis of 460 Pesticides in 10 different Food Commodities by APGC-MS/MS Collaboration with NOFA Lab, Netherlands
  • 43. ยฉ2016 Waters Corporation 43 ๏‚ก Commodity independent โ€“ Semi quantitative screening โ€“ 10 commodities screened against solvent curve ๏‚ก 460 pesticides (92.4 %) passed validation criteria ๏ % Recovery of between 70 and 120 % ๏ % rRSD < 20 % ๏ LoD < 5 ยตg/kg ๏‚ก 32 pesticides (7.6%) failed due to poor analyte recovery (<70%) โ€“ Including nitro- and chloro- phenols, captan and folpet courtesy of NofaLab, the Netherlands, 2015 NOFA Lab โ€“ Analysis of 460 Pesticides in 10 different Food Commodities
  • 44. ยฉ2016 Waters Corporation 44 Method results courtesy of NofaLab, the Netherlands, 2015
  • 45. ยฉ2016 Waters Corporation 45 APGC vs EI: Benefits APGC EI Customer benefit Injection of sample in mg 0.1- 0.5 mg 5- 50 mg (LOD still higher) Inject less, chromatography longer stable Retention times Neglect able shifts (small scan windows) Large shifts (large scan windows) More confidence, less reprocess, save time Response Stable Large variation and sudden drop Less maintenance Cleaning the source Once or twice a year (preventive) Once a week (when needed) No need to vent the system, clean the source, change the filament Replacing the front column/liner (inject less) Every two weeks (preventive) Once or twice a week (when needed) Less downtime Replacing the analytical column (inject less) 3 to 6 months (when needed) Once a month (when needed) Less downtime, save consumable Downtime A week per year (most preventive) One or two months per year (most trouble shooting) Positive ROI Inject Less Clean Less Replace Less Down Less courtesy of NofaLab, the Netherlands
  • 46. ยฉ2016 Waters Corporation 46 ๏‚ก Improved efficiencies for LC and GC amenable multi-residue pesticides analysis on a single instrument platform ๏‚ง Innovative workflow strategies for MS quantification and to maximize laboratory efficiency APGC- MS/MS UPLC- MS/MS Summary โˆ’ IntelliStart โˆ’ QuanPedia โˆ’ TargetLynx XS โˆ’ TrendPlot โˆ’ RADAR โˆ’ PICs
  • 47. ยฉ2016 Waters Corporation 47 Multi-Residue Pesticide Analysis in Food Matrices โ€“ Other Applications Resources: โ€ข LC- and GC- MS/MS pesticides in tea: 720004819en โ€ข LC- MS/MS pesticides in chilli powder: 720005285en โ€ข LC-MS/MS pesticides in okra: 720004789en โ€ข LC- MS/MS pesticides in chilli powder: 720005559en โ€ข GC- MS/MS pesticides in fruits and vegetables: 720004952en โ€ข LC- and GC- MS/MS pesticides in botanicals: 720005659en โ€ขLC- and GC- MS/MS pesticides in ginseng: 720005006en โ€ข Dilute and shoot pesticides in fruit juices: 720004403en โ€ข Food Testing Application Notebook: 720002565en
  • 48. ยฉ2016 Waters Corporation 48 www.waters.com Thank you for your attention Any questions