Analysis of pesticides in food using both LC- and GC-MS/MS, with data and description of Atmospheric Pressure GC, available on the same system as UPLC-MS/MS with rapid changeover.
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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
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Challenges in Multi Residue Pesticide
Analysis of Food Products
Changing
Legislation
Demanding
Performance
Multitude of
Food Types
Variety of
Pesticides
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๏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
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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
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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
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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
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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
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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
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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
โข Intelligent decision making
โข Improves method development
โข Monitor matrix components
โข Detect un-targeted adulterants
๏ก How do I set it up on the instrument?
- Parallel MRM with full scan data acquisition
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โข 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
โข The QuanPediaโข database allows for efficient method management
Select or create LC-MS/MS method
โข TargetLynx XS streamlines automated quantitative data review and reporting
Comprehensive data processing and review
โข Trending inter- and intra-batch QC and sample results over time is easy
with TrendPlot
Compare data day to day, week to week
โข Automated real-time QC checking with QCMonitor prevents wasting
valuable samples
Critical QC Information Delivered Real Time
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IntelliStart: Ready to Use System
๏ก IntelliStart
๏ก In-built Fluidics
๏ก Automated delivery
of reference
solutions
๏ก Automated flow
switching
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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
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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
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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
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Automated Quan Workflow:
QC Monitor
Run samples
Decision time
๏ง Reinject
๏ง Troubleshoot
Criteria defined by the
requirements of your
lab and method
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TrendPlot - Monitoring Long-Term
Robustness
๏ก Long term system
monitoring
๏ก Essential record
for auditors
๏ก Tool for effective
lab management
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๏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
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๏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
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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
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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
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Analysis of 460 Pesticides in 10 different Food
Commodities by APGC-MS/MS
Collaboration with NOFA Lab, Netherlands
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๏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
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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
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๏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
โ IntelliStart
โ QuanPedia
โ TargetLynx XS
โ TrendPlot
โ RADAR
โ PICs
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Multi-Residue Pesticide Analysis in
Food Matrices โ Other Applications
Resources:
โข LC- and GC- MS/MS pesticides in tea: 720004819en
โข LC- MS/MS pesticides in chilli powder: 720005285en
โข LC-MS/MS pesticides in okra: 720004789en
โข LC- MS/MS pesticides in chilli powder: 720005559en
โข GC- MS/MS pesticides in fruits and vegetables: 720004952en
โข LC- and GC- MS/MS pesticides in botanicals: 720005659en
โขLC- and GC- MS/MS pesticides in ginseng: 720005006en
โข Dilute and shoot pesticides in fruit juices: 720004403en
โข Food Testing Application Notebook: 720002565en