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Simultaneous Analysis of Full Scan Method
625 Semi-Volatiles and MRM Method 608
Pesticides by GC-MS/MS in a Single Extract
William Lipps
Analytical & Measuring Instrument Division
Shimadzu Scientific Instruments, Columbia, MD

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Pesticide and Semi-Volatile Analysis Require
Two Extractions and Two Analyses
Pesticides  1000 ml  MeCL2  Hexane
l 608
l 8080
Semi-Volatiles  1000 ml  MeCL2
l 625
l 8270

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Pesticide Requires GC-ECD with Dual Column or
Multiple Detectors for Confirmation
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 min
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00μV(x100,000)
ｸﾛﾏﾄｸﾞﾗﾑ
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 min
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
μV(x100,000)
ｸﾛﾏﾄｸﾞﾗﾑ
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 min
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
μV(x10,000)
ｸﾛﾏﾄｸﾞﾗﾑ

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GCMS (Full Scan or SIM)
Used For Semi-Volatile Analysis
Gas Chromatograph: Separation on a capillary
column, identification by RT, and quantitation
Mass Spectrometer: Positive identification by
matching to a library

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Quadrupole Mass Spectrometer
Ion source
Lenses
Quadrupol
e
Detector
Ion Box:
Fragmentation
& ionization
Lens Stack:
Ion focusing
Quadrupole:
Mass separation
Electron Multiplier:
Ion detection
Entire mass spectrometer is under high vacuum
Make ions Transmit ions Detect ions

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EI Busts Molecules Into Fragments
N
N
CH3
CH3
N
N
CH3
O
O
H
N
N
CH3
CH3
N
N
CH3
O
O
H
e-
m/z=194
m/z=194
m/z=109
m/z=85

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The GCMS Integrates by M/Z at Retention
Time and Provides Spectral Data

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Detected Peaks are Confirmed for
Positive Identification

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N
N
CH3
CH3
N
N
CH3
O
O
H
Mass Spectra is The Fragmentation M/Z
That Elutes at That Time

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Ion
Source
Detector
Ion
Op.cs
Q1:Quadrupole
Detector
Ion
Source
Ion
Op.cs
Q1:Quadrupole
Q2:Collision
Cell
Q3:Quadrupole
Triple Quad Adds a Collision Cell and
Another Quadrupole

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A Collision Cell Takes a Fragment and
Busts it Further
Gas
m/z=109 m/z=56
m/z=53

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Advantages of Triple Quad (MRM)
Over Single Quad (SIM)
CID SIMSIM
Q1 Q3Collision Cell
Selection
Interfering
chemical
Target
Detection
SIM
Selection Selection
Target
CID
Interfering
chemical Detection
MRM（MS/MS)
SIM reduces interference, but
does not completely eliminate it.
MRM eliminates the remaining
interference.

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Triple Quad is Ideal for GCMS Analysis in
Complex Matrices Where SIM is Problematic
MRM
chromatogram
SIM
chromatogram
Time
Intensity
interference ion
Target compound • S/N ratio is enhanced
• Extremely selective for
quantitation
• 10x lower MDL than SIM
• Extended linear range

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SIM and MRM Data Showing Better
Detection and Selectivity by MRM

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GC-MS/MS Multiple Reaction Monitoring
allows us to see lower concentrations with
large dynamic range with less interference.
GC-MS/MS Multiple Reaction
Monitoring

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MRM Quantitation of 0.0005 PPB –
200 PPB Pesticides and Semi-Volatiles

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0.005 PPB Pesticides and
Semi-Volatiles (MRM)

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Advantages and Disadvantages of MRM
Analysis of Pesticides and Semi-Volatiles
Advantages Disadvantages
Sensitive enough for
pesticides analysis
Too sensitive for semi-
volatiles
0.0005 – 200 ppb 0.0005 – 200 ppb
Combine pesticides with
semi-volatile extract?
Do all pesticides extract?

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One Way to Overcome Sensitivity of MRM for
Semi-volatiles is to Extract Less Sample
1000 ml à 0.0005 – 200 ppb
100 ml à 0.005 – 2000 ppb
10 ml à 0.05 – 20,000 ppb (20 ppm)

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Another Way to Overcome Sensitivity of
MRM is to Combine Extracts
Semi-volatile (100 µl)
Pesticide (900 µl)

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Triple Quad Can Operate in
Single Quad Mode and/or Scan/MRM

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Scan (Semi-Volatiles) and MRM Pesticides
100 ppb Semi-volatiles
and 0.005 ppb pesticides

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MRM Peaks Buried in Full Scan
Semi-Volatiles

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Chromatogram Showing MRM
Quantitation of 0.005 PPB DDT

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Chromatogram Showing 0.005 PPB PCB
Congener and MRM Quantitation with Curve

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Method Table Showing Full Scan for
Semi-Volatiles and MRM for Pesticides

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Full Scan for Quantitation of
Benzo (a) Pyrene

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Full Scan Spectra of 10 PPB
Benzo (a) Pyrene (Scan/MRM mode)

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NIST Spectra of Benzo (a) Pyrene

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Advantages of Scan/MRM Quantitation
of Semi-Volatiles and Pesticides
Capable of pesticides/PCB and semi-volatiles in
one injection/extraction:
• 0.0005 – 200 ppb pesticides
• 0.01 – 2000 ppb Semi-Volatiles

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