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Page 2
Business Issues and Challenges
• Global trade increases the number of pesticides to monitor (> several hundreds)– Typically 150-200 on a target list
• Regulation driving lower detection limits– 10 ppb or lower
• Speed: doing more analyses in a day– Fast chromatography and shorter cycle time
• Need for fast startup and long uptime– No method development
Faster Data Review and Reporting
Total Solution Offering
Screen for Unknowns
Page 3
TOTAL Solutions Outline
• Instrumentations and Agilent Portfolio
• GC and LC
• MS Analyzers Selection
• GC/MS
• QQQ (MS/MS)
• LC/Q-TOF
Page 4
Pesticide Analysis Instrumentations
Chromatography (Separation – the best friend of any detector)
• GC – volatile and semi-volatile non-polar compounds
• LC – polar or moderately polar or thermally labile compounds
Detectors
• GC (element selective, FPD, NPD, ECD) – high sensitivity, poor specificity
• LC (UV, FLD) – general purpose, limited sensitivity, poor specificity
• MS –
– SQ: high confidence from spectral confirmation, limited MDL
– QQQ: low detection limits of target compounds in dirty matrices (MRM)
– TOF/Q-TOF: always full spectrum and accurate mass for screening
– TOF-TOF, Q-Trap, …and others (generally not for ROUTINE use).
Page 5
Agilent Has the TOTAL Portfolio for Pesticide Analysis
(semi)-volatile or non-polar
(moderate)-polar or thermally labile
GCFPD/ECD
LCUV, FLD
GC/QDRS
LC/QLC/QQQMRM
GC/QQQMRM
Q-TOFTOF
GAS
LIQUID
Routine Analysis Identify Unknowns
phase
phase
Exact Mass Database Search
pesticides
Page 6
4.296 min.
4.064 min.
4.297 min.
Agilent Unique and Powerful Tools for Pesticide Analysis
GC/MS Retention Time Locked (RTL) Pesticide Libraries
– Pesticide and Endocrine Disruptors library with RT and spectra (926 entries)
– Japanese Positive List library with RT and spectra (430 entries)
Deconvolution Reporting Software
– Extract pesticide spectra from complex matrices
Capillary Flow Technology
– Flow splitting and backflushing
LC/MS METLIN Pesticide database
– with RT, formula, structure and exact mass (>1400 entries)
– To screen for non-target pesticides
Page 7
TOTAL Solutions Outline
• Instrumentations and Agilent Portfolio
• GC and LC
• MS Analyzers Selection
• GC/MS
• QQQ (MS/MS)
• LC/Q-TOF
Page 8
Almost All Pesticides Contain Heteroatoms (Oxygen is too common)
PNH
O
S OO
CH3
CH3
CH3
AcephateN
N N
NH NH
Cl
CH3
CH3 CH3
Atrazine
N+
N+
N
O-
O-
O
O
F
F
F
CH3
CH3
Trifluralin
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Heptachlor
Element-selective GC detectors are commonly used fo r pesticide analysis for sensitivity and selectivity .
Page 9
Sort of Pesticide Instrument Injector column Detector Data system
Organo-Chlorine(CHM) and pyrethroid
GC
Agilent 7890ALS
HP-1 30m×0.25mm×0.25 µm
HP-17 30m×0.25mm×0.25 µm
ECD
ECDAgilent
ChemstationOrgano-
phosphorus(OP)
GC
Agilent 7890ALS
HP-1 30m×0.53mm×1.5 µm
HP-17 30m×0.53mm×1.0 µm
FPD
FPD
Carbamate
Agilent 1200 with
Pickering5200
ALS or manual injector
C8 4.6mm×250mm, 5 µm
C18 4.6mm×250mm, 5 µmFLD
Agilent Chemstation
ConfirmationGC-MS
Agilent 5975ALS HP-5MS 30m×0.32mm×0.5 µm MSD
Agilent Chemstation
Pesticide Residual – CDFA* Instrument Configuration
*California Department of Food and Agriculture
Page 10
2.1x80mm 600 bar RRHT ZORBAX EPA 555 Chlorinated phenoxy acid herbicides
Fast and high resolution
Page 11
TOTAL Solutions Outline
• Instrumentations and Agilent Portfolio
• GC and LC
• MS Analyzers Selection
• GC/MS
• QQQ (MS/MS)
• LC/Q-TOF
Page 12
Guiding Principles in MS Analyzer Selection
The correct choice of analyzer depends on whether one is “LOOKING for UNKNOWNS” or whether one is “CONFIRMING & MEASURING KNOWNS”.
The correct choice of analyzer depends on the COMPLEXITY of the MATRIX.
Page 13
Basic Questions – Which MS Solution
Target analysis only?
Analysis of unknowns?
How much chemical noise from the matrix?
How much sample prep?
Scan or SIM or MS/MS
Scan MS with Quad, IT or TOF
Deconvolution or MS/MS
Backflush or MS/MS
Page 14
Representative Sample
Extraction
Pesticide Workflow: Screen , Confirm and Q uantify
Clean-up
LC/QQQ MRM – for known targets S
C
Q
QuEChERS
S C Q
C16 H19 N3 P ClC15 H25 O P S ClC18 H21 O P Cl
LC/QTOF or TOF Full Spectrum– for unknown compounds
S
Exact Mass Database Search
Molecular Formula Generation
Q C
Another injection for MS/MS (QQQ or QTOF)
GC/MS (PTV) SIM/Scan– for known and unknown Final Report
S
C
Q
Deconvolution
(+backflush)
3 1
3 1
3 1
GC/QQQ MRM – for known targets S
C
Q
Page 15
TOTAL Solutions Outline
• Instrumentations and Agilent Portfolio
• GC and LC
• MS Analyzers Selection
• GC/MS
• QQQ (MS/MS)
• LC/Q-TOF
Page 16
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
TICs of Surface Water Extracts
How many pesticides are in these samples and how long does it take you to confirm?
Page 17
17 Surface Water TICs (Scan): Pesticide Analysis Using DRS with Pesticide Database**
*CDFA is the California Department of Food and Agriculture
CDFA* Agilent DRS
Targets Found (not counting
ISTD)37
Same 37+99 more
False Positives 1 0
Processing Time ~8 hrs 32 min
Saving 7.5 hoursDRS: Deconvolution Reporting Software
**App Note 5989-5076 has the list of all 926 compounds in the database.
September, 2008Page 18
Carbaryl
Peach
Scan at 5.615 min
Deconvoluted/extracted spectrum
Library spectrum
A component in the scan above.
The power of deconvolution is appreciated while comparing the top two spectra (raw scan and the compound spectrum hidden in the raw scan).
Application Note 5989-7670: Replacing Multiple 50-Minute GC and GC-MS/SIM Analyses with One 15-Minute Full-Scan GC-MS Analysis for Non-targeted Pesticides Screening and >10x Productivity Gain
Page 20
TOTAL Solutions Outline
• Instrumentations and Agilent Portfolio
• GC and LC
• MS Analyzers Selection
• GC/MS
• QQQ (MS/MS)
• LC/Q-TOF
Page 21
Analyzers for Trace Target Compounds
LC/QQQ MRM – for known targets S
C
Q
GC/QQQ MRM – for known targets S
C
Q
Who should use QQQ (MS/MS)?
Users doing Selected Ion Monitoring (SIM) for target compound analysis in traditional markets, needing additional sensitivity and selectivity with less sample prep , to meet more demanding analytical requirements.
MRM
Page 22
LC/QQQ - Multiple Reaction Monitoring (MRM) of 301 Compounds
5989-8614EN, includingcompound name, precursor ion and two product ions of all 301 compounds.
Agilent 1200 HPLC With 1.8 micron ZORBAX SB C-18 Column.
Page 23
301 Compounds (Page 1 of 4) - LC/QQQ3,4,5-Trimethacarb Benalaxyl Carbofuran Cycloate
3-Hydroxycarbofuran Bendiocarb Carboxin Cymoxanil
Acephate Benfuracarb Carfentrazone-ethyl Cyproconazole
Acetamiprid Bensulfuron-methyl Chlorbromuron Cyprodinil
Acetochlor Benzoximate Chlorfenvinphos Cyromazine
Acibenzolar-S-methyl Bifenox Chlorfluazuron Daminozide
Aclonifen Bitertanol Chloridazon Deethylatrazine
Alachlor Bromacil Chlorotoluron Deethylterbuthylazine
Aldicarb Bromoxynil Chloroxuron Deisopropylatrazine
Aldicarb Sulfone Bromuconazole 1 Chlorpropham Demeton-S-methyl-sulfone
Aldicarb Sulfoxide Bromuconazole 2 Chlorpyrifos methyl Desmedipham
Aldoxycarb Bupirimate Chlorsulfuron Diazinon
Ametryn Buprofezin Cinosulfuron Dichlofenthion
Aminocarb Butocarboxim Clethodim Dichlofluanid
Anilazine Butocarboxim-sulfoxide Clodinafop-propargyl Dichlorvos
Atrazine Buturon Clofentezine Diclobutrazol
Azamethiphos Butylate Clomazone Diethofencarb
Azinphos-ethyl Carbaryl Cloquintocet-mexyl Difeconazole-1
Azinphos-methyl Carbendazim Coumaphos Difeconazole-2
Azoxystrobin Carbetamide Cyanazine Difenoxuron
Page 24
GC/MS/MS of Aojiru (Kale): Cyfluthrin (4 isomers)
20 ppb Spiked Area: 31007(No.2)
20 ppb Spiked Area: 30815(No.2)
Ashitaba blankArea: 0
1 ppb Spiked Area: 1211(No.2)
5 ppb Spiked Area: 8034(No.2)
20 pg on column
1 pg on column
5 pg on column
20 pg on column
Aojiru : Kale(dried power)
Page 25
GC/MS/MS of Ashitaba Tea:Chlorpyrifos
20 ppb Spiked Area: 88595
20 ppb Spiked Area: 86999
Ashitaba blankArea: 99
1 ppbSpiked Area: 4063
5 ppb Spiked Area: 24284
20 pg on column
1 pg on column
5 pg on column
20 pg on column
Ashitaba (Asian Herb)(dried power)
Sample Quantitation Results - Basil
Run 1 13.3
Run 2 12.2
Run 3 12.8
Run 4 12.5
Run 5 12.5
10 ppb Acephate
Run 1 5.4
Run 2 5.3
Run 3 5.2
Run 4 5.7
Run 5 5.2
5 ppb Quinalphos
Run 1 4.7
Run 2 5.7
Run 3 5.0
Run 4 5.1
Run 5 5.4
5 ppb Chlorfenapyr
Run 1 4.6
Run 2 4.8
Run 3 4.3
Run 4 4.9
Run 5 4.2
5 ppb Endosulfan-beta
Garlic : Single Quad SIM v.s. GC-QQQ MRM
5 ppb Deltamethrin
30 ppb Deltamethrin
GC-Q, SIM GC-QQQ, MRM
This demonstrates that GC-QQQ has much higher selectivity (sensitivity) than GC-Q
Garlic : Single Quad SIM v.s. GC-QQQ MRM
10 ppb Omethoate, MRM
Compound was confirmed easily
40 ppb Omethoate, SIM
Ion ratios were seriously distorted
GC-QQQ removes matrix interference and provides more reliable confirmation
Page 29
TOTAL Solutions Outline
• Instrumentations and Agilent Portfolio
• GC and LC
• MS Analyzers Selection
• GC/MS
• QQQ (MS/MS)
• LC/Q-TOF
Page 30
Business Issues and Challenges
• Global trade increases the number of pesticides to monitor (> several hundreds)– Typically 150-200 on a target list
• Regulation driving lower detection limits– 10 ppb or lower
• Speed: doing more analyses in a day– Fast chromatography and shorter cycle time
• Need for fast startup and long uptime– No method development
Faster Data Review and Reporting
Total Solution Offering
Screen for Unknowns
DRS and Q-TOF to
screen
GC- or LC-QQQ
Deconvolution integrated with
QEdit
• Databases and libraries available
• Universal MassHunter platform
• Backflushing
Page 31
Agilent has the TOTAL portfolio of target and non-target pesticide analyzers
Target Compound Non-target (unknown) Compound
GA
S P
hase
GC/QQQ (MRM)
• MRM method available for >200 compounds
• Backflushing
GC/MSD + Deconvolution
• The only company with deconvolution integrated into data analysis and quantitation (Easy and time saving)
• 2 Pesticide Libraries (for screening and confirmation)
• Backflushing to increase productivity
LIQU
ID P
hase
LC/QQQ (MRM)
• MRM method for >300 compounds
• Optimizer (>500 compounds)
LC/Q-TOF (or TOF) + Exact Mass database search
• Excellent mass accuracy (< 3ppm) to search against public and private databases provides confident results
• Molecular Formula Generator feature reduces data interpretation time
• NEW METLIN databases (1400 entries) for easy screening
Pesticide Analysis Most Popular Application using GCQQQ
• Pesticides in Traditional Chinese Medicine (TCM)
• Exceptional quantitative performance across a wide concentration range
• Exceptional precision for qualitative ion ratios
• Pesticides in carrot
• MS/MS succeeds where SIM has failed
Page 32
Excellent Result for Qualification in Real Sample - Cyanophos in TCM matrix, NOT solvent
•“ Inert” Qualifier Ion Ratio
0.1ppb(LOD)-1000ppb
Page 33
Excellent Result for Quantitation in Real Sample - Cyanophos in TCM matrix, NOT solvent
R^2=0.99940.2ppb(LOQ)-100ppb(9 Points)
•“ Stable” Quant AccuracyEven Up to 1000ppb (~104 linear Range)
Page 34
Build up your confidence in Quantitation Results - 1ppb Bromopropylate in TCM matrix, 10 times lower t han Uniform Limit*
RSD = 5.12%
*10 ppb is the uniform limit in Japan Positive List
Page 35
Chlorpyrifos (28 ppb) Easily Detected and Quantitated by GC/MS/MS – Incurred Carrot
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ts
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onse
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