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0.0
1.0
2.0
3.0
4.0
5.0la
b3
6L
ab
41
La
b3
2L
ab
13
1L
ab
15
La
b6
1L
ab
3la
b6
4L
ab
37
La
b7
9L
ab
6L
ab
14
3L
ab
7L
ab
23
lab
40
lab
38
La
b4
7L
ab
63
La
b5
La
b8
7la
b1
8la
b2
8L
ab
11
9L
ab
13
6la
b3
1la
b9
3L
ab
35
lab
24
La
b6
2la
b1
33
La
b5
1L
ab
13
5L
ab
82
lab
29
lab
56
La
b4
5la
b1
21
lab
68
La
b4
9L
ab
11
La
b5
8la
b1
9L
ab
69
lab
91
lab
57
La
b1
25
La
b7
1la
b5
4la
b5
9L
ab
14
1la
b3
0L
ab
76
La
b9
0L
ab
10
9L
ab
52
La
b1
20
La
b2
0la
b9
lab
85
lab
44
La
b2
6L
ab
10
8L
ab
60
lab
92
La
b1
45
lab
39
La
b9
6la
b3
3L
ab
10
6L
ab
2la
b6
6L
ab
89
lab
14
8L
ab
13
7la
b2
7L
ab
10
4
EUPT-FV11
12% ‘unsatisfactory’
NRLs
79% ‘good’ 9% ‘satisfactory’
SWZ - Category A
Category A: 49% of the Participant Laboratories (72 Laboratories of 147)
63% Good 19 % Satisfactory 18% Unsatisfactory
SWZ - Laboratories in Category A
0,0
1,0
2,0
3,0
4,0
5,036
144
12
53
16
85 6
45
71
114
24
60
47
18
17
57
55
67
41
50
70
30
11
97
15
25
121
19
136
29
113
20
118 5
65
34
61 8
49
110
68
42
66
48
43
28
22
89
81
148
145
133
112
23 9
58 3
52
99
117
134
115
51
122
79
100
46
103
38
139
116
152
NRL
EUPT-FV12
0,0
1,0
2,0
3,0
4,0
5,0La
b0
02
La
b1
36
La
b0
05
La
b0
32
La
b1
50
La
b0
13
La
b0
04
La
b0
97
La
b0
24
La
b1
20
La
b0
96
La
b0
94
La
b0
29
La
b1
45
La
b0
19
La
b0
85
La
b0
08
La
b1
17
La
b0
36
La
b0
73
La
b1
49
La
b1
24
La
b0
76
La
b1
19
La
b1
14
La
b0
50
La
b0
26
La
b0
59
La
b1
09
La
b1
31
La
b0
90
La
b0
92
La
b1
39
La
b1
38
La
b1
21
La
b1
54
La
b0
35
La
b1
05
La
b0
54
La
b0
17
La
b0
18
La
b0
48
La
b0
15
La
b0
64
La
b0
67
La
b0
98
La
b0
78
La
b1
25
La
b0
91
La
b0
11
La
b0
87
La
b1
46
La
b1
37
La
b1
28
La
b1
42
La
b0
37
La
b0
74
La
b0
20
La
b1
41
La
b0
47
La
b0
82
La
b0
23
La
b0
09
La
b0
57
La
b0
99
La
b0
12
La
b1
01
La
b1
30
La
b1
04
La
b0
30
La
b1
08
La
b1
48
La
b0
28
La
b0
49
La
b0
69
La
b0
63
La
b0
79
La
b1
29
La
b1
15
La
b0
40
La
b0
71
NRLsNRLs
77% Good 7 % Satisfactory 16% Unsatisfactory
Category A: 55% of the Participant Laboratories(81 Laboratories of 146)
SWZ RepresentationEUPT-FV13
0,0
1,0
2,0
3,0
4,0
5,0La
b06
0La
b15
6La
b05
8La
b09
9La
b08
1La
b03
9La
b04
3La
b02
6La
b13
5La
b05
4La
b08
4La
b02
1La
b00
5La
b10
5La
b02
5La
b05
9La
b03
3La
b00
3La
b00
9La
b09
6La
b10
1La
b08
7La
b07
7La
b05
6La
b00
6La
b09
2La
b12
8La
b10
0La
b12
3La
b02
4La
b02
3La
b11
7La
b12
0La
b05
0La
b13
4La
b06
1La
b01
8La
b01
7La
b01
2La
b10
9La
b03
5La
b13
7La
b08
8La
b13
1La
b12
6La
b07
8La
b08
5La
b10
2La
b07
0La
b01
9La
b15
1La
b01
5La
b05
2La
b04
8La
b01
4La
b02
8La
b04
5La
b09
4La
b05
5La
b09
7La
b02
9La
b03
8La
b16
7La
b01
1La
b07
1La
b07
5La
b00
1La
b04
2La
b11
8La
b14
4La
b15
5La
b00
2La
b14
9La
b00
4La
b06
2La
b11
2La
b07
2La
b09
3La
b06
3La
b14
6La
b05
3La
b15
7La
b12
7La
b03
6La
b08
6La
b02
7La
b03
2
NRLs
AZ2 Representation
91 % Good 2 % Satisfactory 7 % Unsatisfactory
Category A: 55% of the EU Participant Laboratories
(87 Laboratories of 157 (total 167))
5 NRLs in Cat B
EUPT-FV14
HOW MATRIX EFFECTS AFFECTS TO GC AND LC-MS
ANALYSIS?
-Signal changes
-Abundance of specific fragment ions/trans
-Instrument maintenance
LC-QqQ-MS/MS
Skimer
After 30 tea injections
GC-QqQ-MS Liner after
30 tea injections
4x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
2.6
2.8
+ESI EIC(253.0092) Scan Frag=90.0V 100ppb_Leek_Screening_SinDil.d
Counts vs. Acquisition Time (min)
7.45 7.5 7.55 7.6 7.65 7.7 7.75 7.8 7.85 7.9 7.95 8 8.05 8.1 8.15 8.2 8.25 8.3 8.35 8.4 8.45
Concentration level: 100 ppb
EIC: m/z 253.0092
Demeton-S-Methyl
Orange
Pepper
Solvent
Leek
Signal supression due to matrix effects
Injection 1g matrix/ml
0,E+00
5,E+07
1,E+08
2,E+08
2,E+08
3,E+08
3,E+08
4,E+08
0 50 100 150 200 250 300
Concentration [ppb]
Calibration plots of diazinon (304.6 > 169.0) Solvent
Tomato
Pepper
leek
LC-MS/MS
Common transition
with matrix
Atrazine-2-hydroxy
MRM1 198 156
MRM2 198 86
MRM3 198 114
Std 20 ppb in pear
MRM1 198 156
MRM2 198 86
MRM3 198 114
Sample 114 SM04
Ratio MRM2/MRM1= 36 (43-28)
Ratio MRM3/MRM1= 48 (57-38)
Ratio MRM2/MRM1= 54
Ratio MRM3/MRM1= 31
Pear matrix
LC-QQQ-MS/MS
Secbumeton
MRM1 226 100
MRM2 226 170
MRM3 226 142
MRM1 226 100
MRM2 226 170
MRM3 226 142
Ratio MRM2/MRM1= 87 (104-69)
Ratio MRM3/MRM1= 51 (61-41)
Ratio MRM3/MRM1= 57 (46-68)
Ratio MRM2/MRM1= 164
Ratio MRM3/MRM1= 74
Ratio MRM3/MRM1= 45
Pear matrix
LC-QQQ-MS/MS
Leek Dil10 Standard 100ppb
Ratio 0.6
Triflumuron?
359.2 > 156.0
Triflumuron?
359.2 > 138.9
Ratio 0.7
Triflumuron
359.2 > 156.0
Triflumuron
359.2 > 138.9
-17 Da
-NH3
Cl
NH3
O
Cl
NH
O
NH
OO F
FF
-17 Da
-NH3
Cl
O
?
Triflumuron
6x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
+ESI Scan (9.994 min) Frag=90.0V EUPT_SC_1PPB_PUERRO.d Subtract
* 361.0288* 360.0336
* 359.0409
359.1971
362.0287
358.3313361.1944359.3360 360.2012
Counts vs. Mass-to-Charge (m/ z)
357.8 358 358.2 358.4 358.6 358.8 359 359.2 359.4 359.6 359.8 360 360.2 360.4 360.6 360.8 361 361.2 361.4 361.6 361.8 362 362.2
The fragment and
the isotopic profile of
triflumuron don’t
appear
TRIFLUMURON in LC-TOF-FULL SCAN
EIC 359,0405
6x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
+ESI EIC(359.0405) Scan Frag=90.0V EUPT_SC_1PPB_PUERRO.d Smooth
Counts vs. Acquisition Time (min)
8.6 8.8 9 9.2 9.4 9.6 9.8 10 10.2 10.4 10.6 10.8 11 11.2 11.4 11.6 11.8 12 12.2
TRIFLUMURON 11,22 359,0405 [M+H]+ C15H11ClF3N2O3
TRIFLUMURON Cl37 11,22 361,0375[M+H+2]
+ C15H1137ClF3N2O3
TRIFLUMURON F1 11,22 156,0211 C7H7ClNO
TRIFLUMURON F1 Cl37 11,22 158,0181 C7H737ClNO
3-Chloraniline100 ppb Pear
RT = 2.79 minSM-04 (67 ppb?)
RT = 2.81 min
127>92 127>92
127>88
127>73
127>100127>100
127>73
127>88
127>111 127>111
Ratio 66.2
Ratio 0.20 Ratio 0.20
Ratio 0.91
Ratio 3.21
Ratio 69.6
Ratio 2.65
Ratio 1.37
GC
Q-M
S/M
S
standard sample
Influence of resolution on detection
317.00 317.05 317.10 317.15 317.20 317.25 317.30 317.35
m/z
0
10
20
30
40
50
60
70
80
90
100
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
317.1657
317.2014
317.1728
317.1966
317.1544
NL: 1.89E6
Nar_10ppb_dil5_17500_10micro_1#7268 RT: 9.31 AV: 1 T: FTMS + p ESI Full ms [100.00-800.00]
NL: 1.73E6
Nar_10ppb_dil5_70000_10micro_2#2083 RT: 9.31 AV: 1 T: FTMS + p ESI Full ms [100.00-800.00]
Exact mass of bupirimate 317.1642
Matrix ion. Mass error 27.1 ppm Matrix ion.
Mass error -30.1
ppm
Resolution 17500
Resolution 70000
Two non resolved matrix ions.
Mass error 4.7 ppm
False detect of bupirimate
Orange
mapping of natural components by
Mass
8017 Matrix compoundsm/z: 100-700
Rt: 4-8 min
Co-extracted matrix components LC-TOF-MS of
orange
Miner 3D Enterprise
Co-extracted matrix components of
green-tea9073 Matrix compoundsm/z: 100-700
Rt: 4-10 min
Miner 3D Enterprise
MATRIX EFFECTS
MassData base components- orange matrix
compounds
8017 Matrix compoundsm/z: 100-700
Rt: 4-8 min
m/z: 100-400
Rt: 7-13 min
DB: 227 components
Orange: 2743 matrix
compounds
Miner 3D Enterprise
MATRIX EFFECTS
How can we control or avoid them?
Highly Sensitive
GC/LC-MS
MassData base components- orange matrix
compounds
8017 Matrix compoundsm/z: 100-700
Rt: 4-8 min
m/z: 100-400
Rt: 7-13 min
DB: 227 components
Orange: 2743 matrix
compounds
Miner 3D Enterprise
Mass
Data base components- orange matrix compounds.
Dilution 1:10
5539 Matrix compounds
DB: 227 components
Orange: 1765 matrix compounds Miner 3D Enterprise
Mas
s
Data base components- orange matrix compounds. Dilution
1:50
3479 Matrix compounds
DB: 227 components
Orange: 1082 matrix compounds
MatrixNº of compounds
Rt: 0-17 min
Nº of compounds
Rt: 7-13 min
TIC Area
Rt: 7-13 min
Orange 8017 2743 4.601E+09
Orange 1:10 5539 1765 2.613E+09
Orange 1:50 3479 1082 2.052E+09
Tomato 2408 656 1.93E+09
Peeper 3419 919 2.10E+09
Miner 3D Enterprise
Principal Components Analysis (PCA)
Tomato
Red Onion
Orange
White Onion
No Dilution
No Dilution
No Dilution
No Dilution
Dilution
(1/10 and 1/15)
1. Number of matrix compounds
2. Intensity of matrix compounds
3. Common compounds
Mass Profiler Professional 12.1. Agilent Tech.
Variables
QuEChERS Extraction Method
10 g sample + 10 mL AcN + IS
Add 4 g MgSO4 anhidrous
+ 1 g NaCl + 1 g Na3Citrate·2 H2O
+ 0.5 g Na2HCitrate·1.5 H2O
Centrifugue 5 min. 3500 r.p.m.
Add 750 mg MgSO4
anhidrous. + 125 mg PSA + 125 mg C18
Centrifugue 5 min. 3500 r.p.m.
microLC-MS/MS Analysis
0.033 gr sample/mL injected
Take 5 mL aliquot
Shake 30 second in Vortex
Acidify with 50 μL formic acid 5% in
AcN
Shake automatically 4 min
Take an aliquot add IS and
dilute 1:30 with AcN:H2O (1:9)
Shake automatically 4 min
MatricesTomato, Pepper and Orange
Compounds in the method
1Acetamiprid
2Azinphos-methyl
3Azoxystrobin
4Bitertanol
5Boscalid
6Bromuconazole
7Bupirimate
8Buprofezin
9Carbaryl
10Carbendazim
11Chlorpyrifos
12Cyprodinil
13Diazinon
14Diclorvos-d6 (I.S)
15Dicrotophos
16Diethofencarb
17Difenoconazole
18Dimethoate
19Dimethoate-d6 (I.S)
20Diniconazole
21Diuron
22Dodine
45 Imazalil
46 Imidacloprid
47 Iprodione
48 Iprovalicarb
49 Isoproturon
50 Kresoxim-methyl
51 Linuron-d6 (I.S)
52 Malathion-d10 (I.S)
53 Mandipropamid
54 Metconazole
55 Methidathion
56 Methiocarb
57 Methiocarb Sulfone
58Methiocarb
Sulfoxide
59 Methomyl
60 Methoxyfenozide
61 Omethoate
62 Oxadixyl
63 Oxydemeton-methyl
64 Paclobutrazole
65 Parathion
66 Parathion-Methyl
23Epoxiconazole
24Ethirimol
25Ethofenprox
26Ethoprophos
27Fenamidone
28Fenarimol
29Fenbuconazole
30Fenhexamid
31Fenitrothion
32Fenpropathrin
33Fenpropimorph
34Fenpyroximate
35 Fenthion
36Fenthion Oxon
37 Fenthion Oxonsulfone
38Fenthion
Oxonsulfoxide
39 Fenthion Sulfone
40 Fenthion Sulfoxide
41 Flusilazole
42 Flutriafol
43 Fosthiazate
44 Hexaconazole
67 Penconazole
68 Pencycuron
69 Pendimethalin
70 Phenthoate
71 Phosalone
72 Phoxim
73 Pirimicarb
74 Pirimiphos-methyl
75 Prochloraz
76 Propargite
77 Propiconazole
78 Propoxur
79 Propyzamide
80 Prothiofos
81 Pyraclostrobin
82 Pyrethrins
83 Pyridaben
84 Pyrimethanil
85 Pyriproxyfen
86 Quinoxyfen
87 Rotenone
88 Tebuconazole
89 Tebufenpyrad
90 Tetraconazole
91 Thiodicarb
92 Thiophanate-methyl
93 Tolclofos-methyl
94 TPP (I.S)
95 Triadimefon
96 Triadimenol
97 Triticonazole
98 Zoxamide
Diclorvos-d6
Malathion-d10:
Extraction
TPP
Linuron-d6: Dilution
Dimethoate-d6:
Injection
microLC-QqQ-MS/MSLiquid chromatography
• Column: HALO C18 2.7 μm 90 Å 0.5x50mm
• Mobile phases: Acetonitrile and water (0.1% formic acid)
• Injection volume: 3µl
• Flow: 30 μl/min
• Total run time: 14 min
QqQ-MS• Source: ESI (+) with microFlow
electrode
• Pesticide Identification: 2
transitions
• Source Parameters: Nebulizer and collision gas: nitrogen
Gas temperature: 300ºC
Curtain gas (CUR): 20
IonSpray Voltaje (IS): 5000V
Schedule MRM software features
Collision gas (CAD): Medium
Gradient
0
10
20
30
40
50
60
70
80
90
100
0 2 4 6 8 10 12 14
%
Time (min)
10 min Gradient
Orange 10µg/Kg
µLC
Flow: 30 µL/min
Orange 10µg/Kg
LC
Flow:400 µL/min
Comparison between µLC and LC: Azoxystrobin in an
orange matrix at 10µg/Kg
MRM1: 404372 MRM2: 404344
Peak Area Reproducibility
5 consecutive injections over 3 days of a tomato, orange
and pepper spiked at 10 μg/Kg and 100 μg/Kg and diluted
30 times.
RSD (%) RSD (%)
-
10
20
30
40
50
60
70
80
90
100
<5% 5%-10% 10%-20%
% o
f c
om
po
un
ds
10 µg/Kg
Tomato
Pepper
Orange
-
10
20
30
40
50
60
70
80
90
100
<5% 5%-10% 10%-20%
% o
f c
om
po
un
ds
100 µg/Kg
Tomato
Pepper
Orange
Retention Time Reproducibility
Difference between consecutive injections of tomato, pepper and
orange and standard in solvent spiked at different concentrations
diluted 30 times
-0,15
-0,10
-0,05
0,00
0,05
0,10
0,15
-10 10 30 50 70 90
∆R
t(m
in)
Nº Compounds
0
10
20
30
40
50
60
70
80
90
100
< -50% -50% - (-20%) -20% - 0 0 - 20% 20% - 50% > 50%
% o
f co
mp
ou
nd
s
Tomato
Pepper
Orange
Matrix Effects
Fenitrothio
n
Fenitrothio
n
Methidathion
-
10
20
30
40
50
60
70
80
90
100
ME<20 20<ME<50 ME>50
% o
f co
mp
ou
nd
s
%Matrix effect
Tomato
Pepper
Orange
Principal Components Analysis (PCA)
Tomato
Red Onion
Orange
White Onion
No Dilution
No Dilution
No Dilution
No Dilution
Dilution
(1/15)
1. Number of matrix compounds
2. Intensity of matrix compounds
3. Common compounds
Mass Profiler Professional 12.1. Agilent Tech.
Variables
Real samples from different supermarkets
50 Organic Samples
0
10
20
30
40
50
60
70
80
90
100
Organic samples
% s
am
ple
s
Positives
Positives>10μg/Kg
>MRL
Iprovalicarb
Phenthoate
Propiconazole
Tebuconazole
Iprodione
Prothiofos
Carbendazim
Iprovalicarb
Phenthoate
Prothiofos
Fruit jam samples (51) from various supermarkets
0
10
20
30
40
50
60
70
80
90
100
Perc
en
tag
e o
f S
am
ple
s
Brazil Spain Brazil Brazil Spain Spain
Strawberry J. Grape J. Pineapple J. Peach J. Appricot J. Total
Positive Samples
Positive samples
≥ 10 µg/kg
Negative samples
SiO2SiO2
Zr02
Zirconium oxide-coated Silica Particles
Zr02
Particle size: 100 nm
Relative surface area: >25 m2/g
Zr02/
Y2O3
Particle size: 100 nm
Relative surface area: >100 m2/g
Particle size: 22 μm= 22000 nm
Relative surface area: 310 m2/g
Z-Sep
ZSEP-SIN C18 (55418-U SUPELCO)
The patented zirconia-coated silica particles of Supel QuE Z-
Sep
particle size 22 μm
pore size 14 nm pore size
surface area 310 m2/g
Zirconium(IV) oxide-yttria stabilized (8 mol % yttria as stabilizer)
composition (ZrO2)0.92(Y2O3)0.08
particle size ≤100 nm
surface area >100 m2/g
Absolute height ≥ 10000 counts
PSA+C18
4067 matrix compounds
Co-extracted matrix components of avocado with Z-Sep and PSA+C18. LC-
TOF/MS
PSA+C1
8
Z-
Sep
Z-Sep
2907 matrix compounds
Miner 3D Enterprise
Mass Profiler Professional 12.1. Agilent Tech.
10 Fresh Herbs
Flat
parsley
Chive Coriander Dill
Mint Basil OreganoRosemary Thyme
Curly
parsley
1mL sample + 50 mg
ZSEPDisc format
Particle size: 22 μm= 22000 nm
Relative surface area: 310 m2/g
Cartridge format
-
10
20
30
40
50
60
70
80
90
100
n.d 0-40 41-69 70-120 >120
% c
om
po
un
ds
R (%)
ZSEP
60 mg AcN
40 mg AcN
20 mg AcN
60 mg Pepper
40 mg Pepper
20mg Pepper
-
10
20
30
40
50
60
70
80
90
100
n.d 0-40 41-69 70-120 >120
% c
om
po
un
ds
R (%)
ZrO2-Yttria
60 mg AcN
40 mg AcN
20 mg AcN
60 mg Pepper
40 mg Pepper
20 mg Pepper
Triazoles
Triazole compounds
Bromuconazole
Cyproconazole
Difenoconazole
Diniconazole
Epoxiconazole
Fenbuconazole
Fluquinconazole
Hexaconazole
Metconazole
Penconazole
Propiconazole
Prothioconazole
Tebuconazole
Tetraconazole
Triticonazole
Basil
Chive Coriander
Rosemary4194 Compounds
Total Area5.34 e9
Co-extracted matrix components of Fresh HerbsAbsolute height > 10000 counts LC-TOF-MS
4171 Compounds
Total Area 5.42 e9
4380 Compounds
Total Area 4.70 e9
5364Compounds
Total Area 7.10 e9
LC-TOF-MS Analysis Full Scan Mode
Matrix
QuEChERS
No. compounds Total Area
Chive 5364 7.10E+09
Mint 5100 8.58E+09
Flat Parsley 5070 6.76E+09
Thyme 5054 7.98E+09
Curly Parsley 4843 5.80E+09
Oregano 4644 5.20E+09
Rosemary 4380 6.00E+09
Basil 4194 5.34E+09
Coriander 4171 6.93E+09
Dill 3574 4.51E+09
Co-extracted matrix components of ThymeAbsolute height > 10000 counts LC-TOF-MS
QuEChERS QuEChERS with ZrO2 clean -up
QuEChERS with ChloroFiltr® clean -
up QuEChERS + SPE with ZrO2
5054
Compounds
Total Area 7.98
e9
3725 Compounds
Total Area 5.68 e92824 Compounds
Total Area 3.68 e9
4215
Compounds
Total Area
7.25e9
Co-extracted matrix components of BasilAbsolute height > 10000 counts LC-TOF-MS
QuEChERS QuEChERS with ZrO2 clean -up
QuEChERS with ChloroFiltr® clean -
up QuEChERS + SPE with ZrO2
4194 Compounds
Total Area 5.34 e9
2332 Compounds
Total Area 3.88 e9
1183 Compounds
Total Area 2.70 e9
1976 Compounds
Total Area 2.78 e9
Matrix
QuEChERSQuEChERs +
SPE ZrO2
QuEChERS
(ZrO2 instead
PSA and C18)
QuEChERS
ChloroFiltr®
clean-up
Nº
compounds
Total
Area
Nº
compounds
Total
Area
Nº
compounds
Total
Area
Nº
compounds
Total
Area
Chive 5364 7.10E+09 3820 5.17E+09 4906 7.57E+09 4431 5.91E+09
Mint 5100 8.58E+09 2365 3.36E+09 4614 7.638E+09 3305 4.475E+09
Flat Parsley 5070 7.44E+09 2955 4.14E+09 5014 7.32E+09 4085 5.341E+09
Thyme 5054 7.98E+09 2824 3.68E+09 4215 7.25E+09 3725 5.681E+09
Curly Parsley 4843 5.80E+09 2136 3.03E+09 3485 5.13E+09 3538 4.907E+09
Oregano 4644 5.20E+09 1741 2.22E+09 3016 4.831E+09 2821 3.771E+09
Rosemary 4380 6.00E+09 3030 3.97E+09 4293 6.685E+09 4377 5.676E+09
Basil 4194 5.34E+09 1183 2.69E+09 1976 2.779E+09 2332 3.876E+09
Coriander 4171 6.93E+09 2224 3.88E+09 4041 6.593E+09 3546 6.136E+09
Dill 3574 4.51E+09 1428 2.29E+09 2682 3.842E+09 2388 3.664E+09
LC-TOF-MS Analysis Full Scan Mode
QuEChERS Extraction Method
5 g sample + 5 mL Water+ 10 mL AcN +
IS
Add 4 g MgSO4 anhidrous
+ 1 g NaCl + 1 g Na3Citrate·2 H2O
+ 0.5 g Na2HCitrate·1.5 H2O
Centrifugue 5 min. 3500 r.p.m.
Add 750 mg MgSO4
anhidrous. + 125 mg PSA + 125 mg C18
Centrifugue 5 min. 3500 r.p.m.
Analysis (GC/LC)
0.5 g sample/mL
Take 5 mL aliquot
Shake 30 second in Vortex
Take 1mL aliquot
Shake automatically 4 min
Shake automatically 4 min
SPE 50 mg ZrO2
Acidify with 50 μL formic acid
5% in AcN
1mL sample + 50 mg
ZSEP Disc format
Particle size: 22 μm= 22000 nm
Relative surface area: 310 m2/g
Cartridge format
Matrix QuEChERS QuEChERs + SPE ZrO2
No. compounds Total AreaNo.
compoundsTotal Area
Chive 5364 7.10E+09 3820 5.17E+09
Mint 5100 8.58E+09 2365 3.36E+09
Flat Parsley 5070 6.76E+09 2955 4.14E+09
Thyme 5054 7.98E+09 2824 3.68E+09
Curly Parsley 4843 5.80E+09 2136 3.03E+09
Oregano 4644 5.20E+09 1741 2.22E+09
Rosemary 4380 6.00E+09 3030 3.97E+09
Basil 4194 5.34E+09 1183 2.69E+09
Coriander 4171 6.93E+09 2224 3.88E+09
Dill 3574 4.51E+09 1428 2.29E+09
Orange 4418 6.15E+09 1958 3.91E+09
Tea (Dil 1/5) 4576 9.19E+09 3982 6.49E+09
Tomato 2833 5.28E+09
Lettuce 1586 3.42E+09
Co-extracted matrix components Absolute height > 10000 counts LC-TOF-MS
QuEChERS
QuEChERS + SPE with ZrO2
4194 Compounds
Total Area5.34 e9
1183 Compounds
Total Area 2.70
e9
QuEChERS
QuEChERS + SPE with ZrO2
5054 Compounds
Total Area 7.98
e9
2824 Compounds
Total Area 3.68
e9
Thyme Basil
RECOVERIES at 50 µg/kg
QuEChERS (+ZrO2)
0,0
5,0
10,0
15,0
20,0
25,0
30,0
35,0
40,0
45,0
% o
f C
om
po
un
ds
R (%)
Thyme
0,0
5,0
10,0
15,0
20,0
25,0
30,0
35,0
40,0
45,0
% o
f C
om
po
un
ds
R (%)
Basil
GC (203 Pesticides)
QuEChERS
QuEChERS + SPE ZrO2
%R %R
RECOVERIES at 50 µg/kg
QuEChERS (+ZrO2)LC (155 Pesticides)
QuEChERS
QuEChERS + SPE ZrO2
0,0
5,0
10,0
15,0
20,0
25,0
30,0
35,0
40,0
45,0
50,0
% o
f C
om
po
un
ds
Basil
0,0
5,0
10,0
15,0
20,0
25,0
30,0
35,0
40,0
45,0
% o
f C
om
po
un
ds
Thyme
0
10
20
30
40
50
60
70
80
90
100
n.d 0-40 41-69 70-120 >120
% o
f co
mp
ou
nd
s
R(%)
ORANGE
ZSEP
ZrO2-Yttria
Recoveries at 50 µg/Kg
1 mL spiked orange extract + 40 mg ZSEP/ZrO2-Yttria
cartidges
(conditioning cartidge with 1 mL AcN)
-
10
20
30
40
50
60
70
80
90
100
N.D 0-40 41-69 70-120 >120
% o
f c
om
po
un
ds
R(%)
THYME
ZSEP
ZrO2-Yttria
Recoveries at 50 µg/Kg
1 mL spiked thyme extract + 40 mg ZSEP/ZrO2-Yttria
cartidges
(conditioning cartidge with 1 mL AcN)
2,4-D(0% ZSEP, ZrO2-
Yttria)
Ethirimol(1% ZSEP)
Fluazifop(1% ZSEP, ZrO2-
Yttria)
Haloxyfop(0% ZSEP, ZrO2-
Yttria)
Nitenpyram(0% ZSEP)
Propamocarb(15% ZSEP)
Flufenoxuron (40% ZSEP, ZrO2-
Yttria)
Pendimethalin (15% ZSEP, ZrO2-
Yttria)
Pymetrozine (40% ZSEP, ZrO2-
Yttria)
Recoveries at 50 µg/Kg
1 mL spiked extract + 40 mg ZSEP/ZrO2-Yttria cartidges
(conditioning cartidge with 1 mL AcN)
-
10
20
30
40
50
60
70
80
90
100
nd 0-40 41-69 70-120 >120
% c
om
po
un
ds
ZSEP
Orange 1
Orange 2
Peppermint
Thyme
Oolong Tea
Green Tea
-
10
20
30
40
50
60
70
80
90
100
nd 0-40 41-69 70-120 >120
% c
om
po
un
ds
ZrO2-Yttria
Orange 1
Orange 2
Peppermint
Thyme
Oolong Tea
Green Tea
Thank You
for Your Attention
