Rapid Multiresidue Pesticide Detection in Food
App Note / Case Study
Last Updated: July 10, 2024
(+ more)
Published: June 27, 2024
Credit: iStock
Pesticide residues in agricultural crops, particularly vegetables, are a global concern due to their adverse impacts on human health.
Rapid and high-throughput analytical methods, such as QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe), have streamlined the sample preparation process, enabling efficient analysis of pesticide residues in large numbers of samples.
This application note describes an optimized technique for high-throughput screening and analytical precision and reliability.
Download this application note to:
- Understand the latest advancements in pesticide residue analysis
- Streamline sample preparation processes using the QuEChERS extraction kit.
- Achieve accurate and reliable pesticide residue analysis for food safety assurance.
Application Note
Environmental
Author
Brooke C. Reaser
Agilent Technologies, Inc.
Abstract
Multiresidue pesticide analysis has become one of the most difficult but important
analytical challenges for those using gas chromatography and mass spectrometry.
The Agilent 8890 gas chromatograph (GC) coupled with the Agilent 7010 triple
quadrupole mass spectrometer (GC/TQ) with a high efficiency source 2.0 (HES 2.0)
upgrade is an analytically accurate, robust, and reproducible instrument for
multiresidue pesticide analysis of complex samples. The analysis of 190 pesticides
in a spinach extract was conducted using an Agilent QuEChERS extraction kit across
800 injections. Only GC inlet maintenance was required over the duration of the
injections. The instrument configuration that enabled robust performance included
a multimode inlet, a mid-column backflushing configuration, and the HES 2.0.
No degradation of the analytical method, sensitivity, or instrument performance
occurred, allowing for the high-throughput, accurate, robust, and sensitive detection
of pesticides in spinach.
Enhanced Longevity and
Revolutionized Robustness for the
Sensitive Detection of 190 Pesticides
over 800 Injections
2
Introduction
Multiresidue pesticide analysis remains
an important analytical challenge for
food safety.1-7 Pesticides used to improve
crop yield can end up in the final product,
raising concerns for consumer safety.
As a result, multiple governing bodies
worldwide have published requirements
for the maximum legal residue limit
(MRL) or tolerance for pesticides allowed
in a product. However, the number
of pesticides used in food products
continues to grow as novel chemicals
are introduced, which in turn increases
the complexity of the multiresidue
pesticide analysis.
For especially difficult matrices,
QuEChERS, which stands for quick,
easy, cheap, effective, rugged, and
safe, has become widely accepted as
a sample preparation technique for
multiresidue pesticide analysis.1
Agilent
QuEChERS extraction kits provide
prepackaged dispersive and extraction
products, extraction salts, and ceramic
homogenizers in easy-to-use kits. The
kits are ready-made for various methods,
including methods of the Association of
Official Agricultural Chemists (AOAC)2
and European Standard (EN).3
QuEChERS extracts of food commodities
can be analyzed by either GC or high
performance liquid chromatography
(HPLC) combined with a mass
spectrometer (MS) or tandem mass
spectrometers (MS/MS).4,5 Depending
on the extent of sample cleanup and
the food commodity being analyzed,
QuEChERS extracts can cause
contamination of the instrument,
resulting in poor data quality.6
This
contamination can exhibit as loss
of sensitivity, retention time shifting,
poor peak shape, and more. Regular
maintenance of the instrument, including
GC inlet maintenance, GC column
trimming, and ion source cleaning, is
required to ensure the robustness and
accuracy of the method results.
Backflushing is one of the key practices
in which GC/MS/MS analyses of
complex matrices can be improved.7
Backflushing refers to the reversing
of flows in the capillary column so
that unwanted matrix components
are flushed out of the GC split vent
instead of proceeding to the detector.
Backflushing can provide improved
method robustness and help minimize
the required maintenance of the
mass spectrometer.
Agilent has introduced the new HES 2.0
ion source as part of the 7010D triple
quadrupole mass spectrometer (TQ),
and it is also available as an upgrade
to 7010A/B/C GC/TQ instruments. The
HES 2.0 ion source provides improved
system robustness, allowing the analysis
of hundreds of injections of pesticides in
food matrices with only GC maintenance
and ion source cleaning necessary. The
HES 2.0 delivers the same unparalleled
analytical sensitivity for ultratrace-level
analysis as the original HES.
Multiresidue pesticide analysis in
spinach extract was carried out using
a 7010B GC/TQ upgraded with the
HES 2.0. Matrix-matched standards
were used to analyze and quantify over
400 injections of baby spinach extract
spiked with 50 ppb of multiresidue
standards, demonstrating both method
and instrument robustness. The
multimode inlet (MMI) and backflushing
between two 15 m columns allowed
for minimal downtime for GC inlet
maintenance. Sensitivity and quantitative
accuracy were maintained without
any maintenance performed on the
mass spectrometer.
Experimental
GC/TQ analysis
An 8890 GC with a 7010B TQ system
upgraded with the HES 2.0 was used for
analysis. The instrument and method
were configured as outlined in a previous
application note7
, as shown in Figure 1.
Agilent 7010
with HES 2.0
PSD
(helium)
Agilent 8890
GC
Liquid
Injector
Multimode
inlet
(helium)
HES 2.0
Agilent HP-5ms UI
15 m, 0.25 × 0.25
Figure 1. The Agilent 8890/7010B GC/TQ system upgraded with the HES 2.0 and system configuration.
3
The GC was equipped with an
Agilent 7650A automatic liquid
sampler (ALS) and 50-position tray.
The GC used an MMI to achieve a
temperature-programmed splitless
injection. Mid-column backflush was
carried out using an Agilent Purged
Ultimate Union (PUU) installed between
two identical 15 m columns; the 8890
GC pneumatic switching device (PSD)
module allowed for fewer occurrences
of regular maintenance. The method
parameters are listed in Table 1.
Table 1. Agilent 8890 GC and Agilent 7010B upgraded with the HES 2.0 ion source conditions for pesticide analysis.
GC
Instrument Agilent 8890 with Fast Oven, Auto Injector
and Tray
Inlet Multimode Inlet (MMI)
Mode Splitless
Purge Flow to Split Vent 15 mL/min at 0.75 min
Septum Purge Flow 3 mL/min
Septum Purge Flow Mode Switched
Injection Volume 1.0 µL
Injection Type Standard
L1 Air Gap 0.1 µL
Gas Saver Off
Inlet Temperature 60 °C for 0.1 min, then to 280 °C at 600 °C/min
Postrun Inlet Temperature 310 °C
Postrun Total Flow 25 mL/min
Carrier Gas Helium
Inlet Liner Agilent Ultra Inert 2 mm dimpled
liner (p/n 5190‑2297)
Oven
Initial Oven Temperature 60 °C
Initial Oven Hold 1 min
Ramp Rate 1 40 °C/min
Final Temperature 1 170 °C
Final Hold 1 0 min
Ramp Rate 2 10 °C/min
Final Temperature 2 310 °C
Final Hold 2 3 min
Total Run Time 20.75 min
Postrun Time (Backflushing) 1.5 min
Equilibration Time 3 min
Column 1
Type Agilent HP-5ms UI (p/n 19091S-431UI)
Length 15 m
Diameter 0.25 mm
Film Thickness 0.25 µm
Control Mode Constant flow
Flow 1.00 mL/min
Inlet Connection Multimode inlet (MMI)
Outlet Connection PSD (PUU)
PSD Purge Flow 5 mL/min
Postrun Flow (Backflushing) –7.873 mL/min
Column 2
Type Agilent HP-5ms UI (p/n 19091S-431UI)
Length 15 m
Diameter 0.25 mm
Film Thickness 0.25 µm
Control Mode Constant flow
Flow 1.200 mL/min
Inlet Connection PSD (PUU)
Outlet Connection MSD
Postrun Flow (Backflushing) 8.202 mL/min
MSD
Model Agilent 7010B
Source Agilent HES 2.0
Vacuum Pump Performance turbo
Tune File Atunes.eihs.tune.xml
Solvent Delay 3 min
Quad Temp (MS1 and MS2) 150 °C
Source Temperature 280 °C
Mode dMRM or Scan
He Quench Gas 4 mL/min
N2
Collision Gas 1.5 mL/min
MRM Statistics
Total MRMs (dMRM mode) 552
Minimum Dwell Time (ms) 2.63
Minimum Cycle Time (ms) 82.42
Maximum Concurrent MRMs 48
EM Voltage Gain Mode 10
4
The Agilent Pesticide and Environmental
Pollutant (P&EP) database (P&EP 4,
part number G9250AA) was used to
easily and rapidly create the dynamic
multiple reaction monitoring (dMRM)
method. This method, which enabled the
analysis of 190 pesticides with a total
of 552 MRMs, resulted in a maximum
of 48 concurrent MRMs, as shown in
Figure 2.
QuEChERS sample preparation
The sample preparation procedure is
summarized in Figure 3. A bag of frozen
organic baby spinach was homogenized
using a spice grinder. Then, eight
replicates were prepared. For each
replicate, 15 g of the homogenized
spinach were weighed into a 50 mL
test tube. Then, two of the replicates
were designated as samples, while the
remaining six were designated for pooled
matrix-matched standards. Fifteen
microliters of the internal standard
mixture (part number 5190-0502)
diluted to 50 ng/µL was added to the
two spinach samples. To all eight
replicates, 15 mL of 1% acetic acid in
acetonitrile was added and the mixture
was vortexed until well mixed. To each
Figure 2. Concurrent MRMs versus retention time.
Retention time (min)
Concurrent MRMs
0
4
8
12
16
20
24
28
32
36
40
44
48
52
4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Figure 3. Sample preparation workflow.
QuEChERS
extraction kit
Agilent
QuEChERS
dispersion kit
15 g of spinach
+ 15 mL of ACN with 1% AA,
vortex
Take 8 mL
supernatant
Shake and
centrifuge
Shake and
centrifuge
Dilute, spike, and
prepare in-vial
Sample analysis
on GC/TQ
5
50 mL tube, the salt packet and two
homogenizers from the QuEChERS kit
(part number 5982-5755) were added
for extraction. These were shaken for
1 minute, then centrifuged at 4,000 rpm
with a maximum radius of 17.4 cm
for 5 minutes. For the samples and
the pooled standards, 8 mL of the
supernatant was transferred to a
tube with salt for dispersion using the
QuEChERS kit (part number 5982-5058).
These were shaken for 30 seconds then
centrifuged as before for 5 minutes. The
supernatant for each of the samples
was removed and placed in an amber
glass vial. For the pooled standards,
the supernatant of all replicates was
removed and mixed in a large amber jar
for standard preparation.
Standard preparation
The multiresidue matrix-matched
standards were created from the
FDA analytical reference standards
kit (part number PSM-101). Mixes
A, B, C, D, E, L, M, N, O, and P from
the PSM-101 pesticides mix were
combined to create a 10 ppm stock
standard of 190 pesticide residues.
The stock solution was then diluted
in acetonitrile down to the following
nominal concentrations: 1,000, 100, 10,
and 1 ppb. In a GC vial, the standards
were combined with the spinach
extract. The internal standard mixture
of parathion-d10 and alpha-BHC-d6
, and
acetonitrile were combined until the
nominal concentration of the internal
standard was 50 ppb and the nominal
concentrations of the matrix-matched
standards in a total volume of 1,500 µL
were as follows: 0.1, 0.5, 1, 5, 10, 50,
100, 253.3, 500, and 1,000 ppb. Extra
vials of the 50-ppb matrix-matched
standard were made for quantification
to test robustness. The samples were
diluted by a factor of three in the vials
to match the matrix concentration in
the standards. This 3x dilution factor
was determined by analyzing the matrix
alone in full scan mode as described in a
previous application note7
to ensure that
the instrument was not overloaded or
saturated by the matrix. Vials with 250 µL
glass inserts were used with 100 µL
of each standard or sample in-vial for
GC analysis.
Sequence
Each sequence included 102 injections
of spinach extract, either as a sample
or matrix-matched standard. Additional
injections of blank acetonitrile were
used to evaluate system cleanliness
by ensuring no analyte carryover or
additional background contamination. A
representative MRM chromatogram of
the 50-ppb matrix-matched standards
in spinach extract is shown in Figure 4A
with a zoomed in portion shown in
Figure 4B. The sequence included:
– Matrix-matched calibration curve
(10 pts)
– Two spinach samples
– Matrix-matched calibration curve
(10 pts)
– Matrix-matched standards (50 ppb) ×
60 times
– Matrix-matched calibration curve
(10 pts) × 2 times, each standard in
duplicate
Figure 4. A representative chromatogram (A) and a zoomed in portion of the chromatogram (B).
×108
A
Acquisition time (min)
Counts
4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
×107
B
Acquisition time (min)
Counts
5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
6
To achieve more than 400 injections of
the 50 ppb matrix-matched standard,
seven sequences were run for a total
of 819 injections, of which 714 were
spinach matrix injections. After each
sequence, the GC inlet liner and septum
were changed, and the 5 µL syringe
was changed as necessary. Also, the
GC vials were refreshed with samples
and standards that had been stored in
the freezer. No additional instrument
maintenance was performed.
Results and discussion
Of the 190 pesticide residues analyzed
by GC/TQ, 114 were selected for further
study based on their analytical response
and performance. These 114 residues
were chosen because their calibration
curves were either linear or quadratic
throughout the seven sequences. These
curves did not require extensive analyst
intervention, such as manual integration,
and had calibration curves that
encompassed the 50 ppb point so that
the 50 ppb matrix-matched standards
for robustness could be calculated as
samples. Any points on the calibration
curve that had signal-to-noise (S/N) < 3,
were interfered with by contaminants,
or had accuracy greater than or equal to
± 25% were excluded (≥ ± 25%). A table
summarizing these residues can be
found at the end of the application note
in Table 2.
Many of the pesticide residues could
accurately be quantified down to 0.5
or 0.1 ppb while maintaining S/N > 10
and quantification accuracy of < 25%.
For example, Figures 5A, 5B, and 5C
show the 0.1 ppb peak, corresponding
qualifiers, and calibration curve of DCPA,
respectively. The data are defined well
by a quadratic calibration curve over
the calibration range 0.1 to 1,000 ppb
through four orders of magnitude.
DCPA has many MRLs as defined by the
US FDA down to 50 ppb in various fruits
and vegetables.
Figure 5. Integrated peak (A) and qualifiers (B) of the 0.1 ppb peak of DCPA as well as the full calibration
curve (C).
×103
×102
A
B
×10 C 1
Acquisition time (min)
Counts
+ MRM CID at 25.0 (298.9 & 221.0)
10.26 10.28 10.30 10.32 10.34 10.36 10.38 10.40 10.42 10.44
Acquisition time (min)
10.26 10.28 10.30 10.32 10.34 10.36 10.38 10.40 10.42 10.44
-0.2
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
10.325 min
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
298.9 & 221.0
300.9 & 223.0
331.8 & 300.9
Ratio = 89.2 (95.1%)
Ratio = 42.0 (97.0%)
DCPA
Relative concentration
0 1 2 3 4 5 6 7 8 9 10
-0.2
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
y = -0.013350x2
+ 2.835571x + 0.001611
R2
= 0.99899365
R = 0.99969055
Weight: 1/x
Relative abundance (%) Relative responses
7
Figures 6A and 6B show the chlorpyrifos
0.5 ppb peak and qualifiers (respectively),
while Figure 6C shows the corresponding
calibration curve. The curve is linear
through 3.5 orders of magnitude and
chlorpyrifos has MRLs in various food
commodities, the lowest of which is
0.01 ppm in food items such as egg, fig,
grape, and apple.
Figure 6. Integrated peak (A), qualifiers (B) of the 0.5 ppb peak of chlorpyrifos as well as the full calibration
curve (C).
×104
×102
A
B
×10 C 1
Acquisition time (min)
Counts
Relative concentration
Relative abundance (%) Relative responses -0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
196.9 & 169.0
198.9 & 171.0
313.8 & 257.8
Ratio = 103.0 (108.4%)
Ratio = 43.1 (98.7%)
+ MRM CID at 15.0 (196.9 & 169.0)
10.16 10.18 10.20 10.22 10.24 10.26 10.28 10.30 10.32
Acquisition time (min)
10.16 10.18 10.20 10.22 10.24 10.26 10.28 10.30 10.32
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
10.220 min Chlorpyrifos
0 1 2 3 4 5 6 7 8 9 10
-0.2
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
y = 2.182005x + 0.002352
R2
= 0.99501738
R = 0.99950640
Weight: 1/x2
8
In terms of spinach MRLs, Figures 7, 8,
and 9 provide three examples. Figure 7
shows the results for bifenthrin, which
is quadratic through 3.5 orders of
magnitude down to 0.5 ppb and has an
MRL of 0.2 ppm in spinach. Diazinon,
linear through 3.5 orders of magnitude
down to 0.5 ppb, is shown in Figure 8,
with an MRL in spinach of 0.7 ppm.
Figure 7. Integrated peak (A), qualifiers (B) of the 0.5 ppb peak of bifenthrin as well as the full calibration
curve (C).
×104
×102
A
B
×10 C 2
Acquisition time (min)
Counts
Relative concentration
Relative abundance (%) Relative responses
Bifenthrin
0 1 2 3 4 5 6 7 8 9 10
-0.2
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
y = 0.459107x2
+ 18.988674x + 0.012908
R2
= 0.99465789
R = 0.99640909
Weight: 1/x2
+ MRM CID at 25.0
(181.2 & 165.2)
14.14 14.16 14.18 14.20 14.22 14.24 14.26 14.28 14.30 14.32
Acquisition time (min)
14.14 14.16 14.18 14.20 14.22 14.24 14.26 14.28 14.30 14.32
2
3
4
5
6
7
8
14.202 min
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
181.2 & 165.2
181.2 & 166.2
166.2 & 165.2
Ratio = 87.4 (109.7%)
Ratio = 52.5 (107.2%)
9
Figure 8. Integrated peak (A), qualifiers (B) of the 0.5 ppb peak for diazinon as well as the full calibration
curve (C).
×103
×102
A
B
C
Acquisition time (min)
Counts
Relative concentration
Relative abundance (%) Relative responses
Diazinon
0 1 2 3 4 5 6 7 8 9 10
0
1
2
3
4
5
6
7
8 y = 0.638177x – 3.640200E-004
R2 = 0.98721937
R = 0.99294761
Weight: 1/x2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
137.1 & 84.0
199.1 & 93.0
Ratio = 64.7 (96.5%)
+ MRM CID at 10.0 (137.1 & 84.0)
8.44 8.46 8.48 8.50 8.52 8.54 8.56 8.58 8.60 8.62
Acquisition time (min)
8.44 8.46 8.48 8.50 8.52 8.54 8.56 8.58 8.60 8.62
0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
8.523 min
10
Lastly, boscalid is shown in Figure 9
with an MRL of 1 ppb; it is easily defined
by a quadratic curve with four orders
of magnitude down to 0.1 ppb. In the
spinach sample, all three residues fell
below the limit of quantification (LOQ) of
the analytical method, and below their
respective spinach MRLs. In the spinach
samples, both boscalid and bifenthrin
fell below the limit of detection (LOD) as
no peak was detected for either residue.
However, a small amount of diazinon
was detected that was not present in
the solvent blank. However, the area of
the peak fell well below the LOQ and had
an S/N very close to 3, and therefore
approached or fell below the LOD.
×103
×102
×102
A
B
C
Acquisition time (min)
Counts
Relative concentration
Relative abundance (%) Relative responses
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
140.0 & 112.0
140.0 & 76.0
111.9 & 76.0
Ratio = 87.0 (104.4%)
Ratio = 32.9 (99.3%)
+ MRM CID at 10.0 (140.0 & 112.0)
16.84 16.86 16.88 16.90 16.92 16.94 16.96 16.98 17.00 17.02
Acquisition time (min)
16.84 16.86 16.88 16.90 16.92 16.94 16.96 16.98 17.00 17.02
0
1
2
3
4
5
6
7
Boscalid 16.909 min
0 1 2 3 4 5 6 7 8 9 10
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
y = 0.635140x2
+ 8.900401x + 0.002796
R2
= 0.97434891
R = 0.99281390
Weight: 1/x2
Figure 9. Integrated peak (A), qualifiers(B) of 0.1 ppb peak of boscalid as well as the full calibration
curve (C).
11
The innovative HES 2.0 source enabled
enhanced response stability for the
analyzed pesticides over 400 replicate
injections of the matrix-matched
calibration standard at 50 ppb
analyzed within a sequence with over
800 total injections. Figure 10 shows
the 400 replicates of the 50 ppb
matrix-matched standard, calculated
as samples from the corresponding
calibration curves across six sequences.
The X-axis on the top corresponds to the
number of injections of just the 50 ppb
matrix-matched standard for robustness.
The lower X-axis corresponds to the total
injection number of spinach QuEChERS
matrix, and therefore excludes blank
injections. The concentration in ppb
versus injection number plot shows
how robust and accurate the analysis
was. The results showed all but one
point falling within ± 20% error, the
usual % error given by GC/TQ data, and
most points well within ± 10% of the
actual. The %RSD for 400 replicates
of all 114 residues are summarized
in Table 2, with nearly 80% of the 114
residues having %RSD < 10%, and only
five having %RSD above 20%. The
robustness of the analysis and the
instrument is clearly shown, with only
inlet maintenance required between
sequences and no further maintenance
of the instrument needed.
Figure 10. Calculated concentration of pesticides in 50 ppb matrix-matched standard over the course of
714 injections of spinach QuEChERS extract.
0 50 100 150 200 250 300 350 400
30
35
40
45
50
55
60
65
70
23 73 165 257 349 441 533 583 675
Adjusted 50 ppb spiked standard injection number
ppb
QuEChERS injection number
Parathion
BHC-alpha (benzene hexachloride)
Pentachlorobenzonitrile
Pentachlorothioanisole
Fenthion
12
Table 2. Summary of 114 residues, including calibration range, calibration curve fit, and %RSD over the 400 injections
of 50 ppb matrix-matched standard injections for robustness. Those results with %RSD > 20% are highlighted in red.
Name
Retention Time
(minutes)
Min Cal
(ppb)
Max Cal
(ppb) Curve Fit Curve Weight %RSD
Ethiolate 4.609 0.5 1,000 Linear 1/x2 7.6
Dichlorvos 4.826 0.5 1,000 Quadratic 1/x 10.4
Nicotine 5.424 0.5 1,000 Linear 1/x2 11.9
Biphenyl 5.615 1 1,000 Linear 1/x2 6.2
2-Phenylphenol 6.457 5 1,000 Quadratic 1/x 7.5
Pentachlorobenzene 6.566 0.1 1,000 Linear 1/x2 4.8
Tecnazene 7.118 0.1 1,000 Linear 1/x2 3.9
Diphenylamine 7.186 0.1 1,000 Quadratic 1/x2 6.5
Ethoprophos 7.238 5 1,000 Quadratic 1/x 12.3
2,3,5,6-Tetrachloroaniline 7.297 0.5 1,000 Linear 1/x2 4.9
Chlorpropham 7.325 0.5 1,000 Quadratic 1/x 7.5
Trifluralin 7.462 1 1,000 Quadratic 1/x2 6.6
Benfluralin 7.496 0.1 1,000 Quadratic 1/x2 7.2
BHC-alpha (Benzene Hexachloride) 7.881 1 1,000 Linear 1/x2 1.0
2,6-Diisopropylnaphthalene 8.02 5 1,000 Quadratic 1/x 5.5
Hexachlorobenzene 8.024 0.5 1,000 Quadratic 1/x 4.5
Ethoxyquin 8.034 0.1 1,000 Quadratic 1/x2 25.3
Dichloran 8.04 1 250 Linear 1/x2 7.7
Simazine 8.043 5 1,000 Linear 1/x2 7.0
Pentachloroanisole 8.073 0.1 1,000 Linear 1/x2 3.3
Atrazine 8.124 1 1,000 Linear 1/x2 5.5
Beta-BHC 8.278 1 1,000 Linear 1/x2 4.9
Terbuthylazine 8.363 1 1,000 Linear 1/x2 14.6
BHC-gamma (Lindane, Gamma HCH) 8.398 1 1,000 Linear 1/x2 4.5
Pentachloronitrobenzene 8.478 0.5 1,000 Quadratic 1/x2 33.7
Pentachlorobenzonitrile 8.515 0.1 1,000 Quadratic 1/x2 3.1
Diazinon 8.526 0.5 1,000 Linear 1/x2 5.8
Pyrimethanil 8.53 0.1 1,000 Linear 1/x2 5.0
BHC-delta 8.763 1 1,000 Quadratic 1/x 11.4
Triallate 8.817 1 1,000 Quadratic 1/x2 4.4
Iprobenfos 8.942 0.5 1,000 Quadratic 1/x2 17.3
Pirimicarb 8.976 1 1,000 Linear 1/x2 8.9
Pentachloroaniline 9.178 0.1 1,000 Linear 1/x2 4.6
Propanil 9.193 0.5 1,000 Quadratic 1/x2 11.4
Metribuzin 9.256 0.5 1,000 Quadratic 1/x2 5.8
Dimethachlor 9.255 0.5 1,000 Linear 1/x2 6.0
Vinclozolin 9.372 0.1 1,000 Linear 1/x2 9.5
Chlorpyrifos-methyl 9.404 0.1 1,000 Quadratic 1/x2 8.4
Parathion-methyl 9.403 5 1,000 Quadratic 1/x 9.3
Ametryn 9.495 0.5 1,000 Quadratic 1/x2 6.5
Tolclofos-methyl 9.496 5 1,000 Linear 1/x2 5.8
Prometryn 9.541 0.1 1,000 Quadratic 1/x2 6.9
Pirimiphos-methyl 9.85 0.5 1,000 Quadratic 1/x2 8.9
Fenitrothion 9.855 0.1 1,000 Quadratic 1/x2 10.2
13
Name
Retention Time
(minutes)
Min Cal
(ppb)
Max Cal
(ppb) Curve Fit Curve Weight %RSD
Ethofumesate 9.877 0.5 1,000 Quadratic 1/x2 6.5
Malathion 9.995 10 1,000 Quadratic 1/x 20.0
Pentachlorothioanisole 10.032 0.1 1,000 Linear 1/x2 3.5
Metolachlor 10.166 5 1,000 Linear 1/x2 6.2
Fenthion 10.187 0.5 1,000 Linear 1/x2 2.4
Chlorpyrifos 10.224 0.5 1,000 Linear 1/x2 4.5
Parathion 10.242 1 1,000 Linear 1/x2 2.7
Triadimefon 10.275 0.5 1,000 Quadratic 1/x 11.6
Tetraconazole 10.319 0.5 1,000 Quadratic 1/x2 7.5
DCPA (Dacthal, Chlorthal-dimethyl) 10.328 0.1 1,000 Quadratic 1/x 7.3
Isocarbophos 10.346 0.1 1,000 Linear 1/x2 4.7
Butralin 10.496 0.5 1,000 Linear 1/x2 5.7
Cyprodinil 10.672 0.5 1,000 Linear 1/x2 7.8
MGK-264 10.709 0.1 1,000 Linear 1/x2 7.3
Pendimethalin 10.797 0.5 1,000 Linear 1/x2 4.6
Penconazole 10.826 0.5 1,000 Quadratic 1/x2 9.8
Heptachlor Exo-epoxide 10.904 10 1,000 Quadratic 1/x 14.1
Fipronil 10.915 0.5 1,000 Quadratic 1/x 10.7
Triadimenol 11.008 0.5 1,000 Quadratic 1/x2 7.1
Quinalphos 11.01 1 1,000 Linear 1/x2 3.3
Chlordane-trans 11.326 100 1,000 Quadratic 1/x 13.6
DDE-o,p' 11.363 0.1 500 Quadratic 1/x2 11.8
Mepanipyrim 11.458 0.5 1,000 Linear 1/x2 7.1
Flutriafol 11.596 0.5 1,000 Quadratic 1/x 6.6
Flutolanil 11.664 0.5 1,000 Quadratic 1/x2 4.6
Napropamide 11.697 0.5 1,000 Linear 1/x2 8.5
Hexaconazole 11.73 0.5 1,000 Linear 1/x2 8.6
Isoprothiolane 11.776 0.1 1,000 Linear 1/x2 4.8
Prothiofos 11.782 0.5 1,000 Linear 1/x2 5.2
Fludioxonil 11.819 0.5 1,000 Quadratic 1/x2 6.9
DEF 11.871 0.5 1,000 Linear 1/x2 7.4
DDE-p,p' 11.91 0.1 500 Quadratic 1/x2 9.8
Oxyfluorfen 11.988 0.5 1,000 Linear 1/x2 5.2
Myclobutanil 12.013 0.5 1,000 Quadratic 1/x2 8.2
Buprofezin 12.066 1 1,000 Quadratic 1/x2 6.2
Bupirimate 12.089 0.5 1,000 Linear 1/x2 6.7
Kresoxim-methyl 12.093 0.5 1,000 Quadratic 1/x 5.9
Chlorfenapyr 12.326 0.5 1,000 Quadratic 1/x2 4.8
Endrin 12.425 5 1,000 Quadratic 1/x 10.3
Ethion 12.718 5 1,000 Linear 1/x2 7.5
Benalaxyl 13.167 0.5 1,000 Quadratic 1/x2 7.7
Trifloxystrobin 13.223 0.5 1,000 Linear 1/x2 5.3
Quinoxyfen 13.222 0.1 1,000 Linear 1/x2 7.7
Endosulfan Sulfate 13.328 1 1,000 Quadratic 1/x2 13.2
Tebuconazole 13.565 0.5 1,000 Quadratic 1/x2 6.6
Nuarimol 13.595 0.5 1,000 Quadratic 1/x2 6.4
Triphenyl Phosphate 13.659 0.5 1,000 Quadratic 1/x2 6.1
14
Name
Retention Time
(minutes)
Min Cal
(ppb)
Max Cal
(ppb) Curve Fit Curve Weight %RSD
Piperonyl butoxide 13.662 0.5 1,000 Quadratic 1/x2 5.9
Epoxiconazole 13.876 0.5 1,000 Quadratic 1/x2 8.5
Spiromesifen 14.014 1 1,000 Quadratic 1/x 15.5
Tetramethrin I 14.207 0.5 1,000 Quadratic 1/x 7.4
Bifenthrin 14.179 0.5 1,000 Quadratic 1/x2 4.4
EPN 14.226 10 1,000 Quadratic 1/x2 5.8
Bromopropylate 14.221 0.5 1,000 Quadratic 1/x2 5.2
Etoxazole 14.375 0.5 1,000 Quadratic 1/x2 6.3
Tebufenpyrad 14.398 0.5 1,000 Quadratic 1/x2 6.9
Fenamidone 14.449 0.5 1,000 Quadratic 1/x2 7.4
Tetradifon 14.72 5 1,000 Quadratic 1/x2 9.2
Metrafenone 15.648 0.5 1,000 Quadratic 1/x2 6.4
Bitertanol I 15.857 0.5 1,000 Quadratic 1/x2 9.7
Spirodiclofen 15.976 5 1,000 Quadratic 1/x2 49.3
Pyridaben 16.081 0.5 1,000 Quadratic 1/x2 5.8
Cyfluthrin I 16.484 5 1,000 Quadratic 1/x2 22.2
Fenbuconazole 16.535 5 1,000 Quadratic 1/x2 9.5
Cypermethrin I 16.8 5 1,000 Quadratic 1/x 23.8
Boscalid 16.909 0.1 1,000 Quadratic 1/x2 8.4
Ethofenprox 17.096 0.5 1,000 Quadratic 1/x2 5.9
Difenoconazole I 18.148 1 1,000 Quadratic 1/x 12.4
Azoxystrobin 18.787 10 1,000 Quadratic 1/x2 11.2
Dimethomorph I 19.175 5 1,000 Quadratic 1/x 15.3
www.agilent.com
DE34182072
This information is subject to change without notice.
© Agilent Technologies, Inc. 2024
Printed in the USA, May 3, 2024
5994-7385EN
Conclusion
The analytical performance of the
Agilent 7010 Series triple quadrupole
mass spectrometer (GC/TQ) upgraded
with the HES 2.0 electron ionization
(EI) source was demonstrated for
multiresidue pesticide analysis. The
system demonstrates analytical
sensitivity as the same or better
than the original HES as well as
excellent accuracy and robustness.
The 7010 GC/TQ with HES 2.0,
coupled with an Agilent 8890 GC
with an MMI inlet and 15 m × 15 m
mid-column backflush configuration
minimizes instrument downtime
by allowing for inlet maintenance
without requiring the cooling of the
heated zones. With no impact to the
analytical method or degradation
of the instrument performance, this
application demonstrates the ability of
the instrument to provide robust and
reliable analytical results, including for
challenging matrices.
References
1. Anastassiades, M.; Lehotay, S. J.;
Stajnbaher, D.; Schenck, F. J. Fast and
Easy Multiresidue Method Employing
MeCN Extraction/Partitioning and
“Dispersive Solid-Phase Extraction”
for the Determination of Pesticide
Residues in Produce. J. AOAC Int.
2003, 86, 412− 431.
2. Pesticide Residues in Foods by
MeCN Extraction and Partitioning
with Magnesium Sulfate. Official
Methods of Analysis of AOAC
International; AOAC International:
Gaithersburg, MD, 2007; Method
2007.1.
3. Lehotay, S. J. QuEChERS Sample
Preparation Approach for Mass
Spectrometric Analysis of Pesticide
Residues in Foods. Methods
Mol. Biol. 2011, 747, 65–91. doi:
10.1007/978-1-61779-136-9_4.
PMID: 21643905.
4. Alder, L.; Greulich, K.; Kempe, G.;
Vieth, B. Residue Analysis of 500
High Priority Pesticides: Better
by GC-MS or LC–MS/ MS? Mass
Spectrom. Rev. 2006, 25, 838–865.
5. Chamkasem, N.; Ollis, L. W.;
Harmon, T.; Lee, S.; Mercer, G.
Analysis of 136 Pesticides
in Avocado Using a Modified
QuEChERS Method with LC-MS/MS
and GC-MS/MS. J. Agric. Food Chem.
2013, 61(10), 2315–2329. DOI:
10.1021/jf304191c
6. Lehotay, S. J.; Han, L.;
Sapozhnikova, Y. Automated
Mini-Column Solid-Phase Extraction
Cleanup for High-Throughput
Analysis of Chemical Contaminants
in Foods by Low-Pressure Gas
Chromatography-Tandem Mass
Spectrometry. Chromatographia
2016, 79(17), 1113–1130. DOI:
10.1007/s10337-016-3116-y.
7. Andrianova, A.; Zhao, L. Five Keys to
Unlock Maximum Performance in
the Analysis of Over 200 Pesticides
in Challenging Food Matrices by
GC/MS/MS. Agilent Technologies
application note, publication number
5994-4965EN, 2022.
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