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Residual Pesticides Analysis of Botanical Ingredients Using Gas Chromatography Triple Quadrupole Mass Spectrometry

Riki Kitano1, Tairo Ogura1, Nicole Lock1, Robert Clifford1, Julie Kowalski2, Jack Cochran2, Dan Li2
1. Shimadzu Scientific Instruments, Inc. 2. Restek Corporation

Originally published by Shimadzu Corporation in collaboration with Restek Corporation.

Introduction

The use of dietary supplements is increasing in the United States. These dietary supplements are made from various dried botanicals, which may contain residual pesticides from agricultural practices, and because of that, they have to be monitored to ensure their quality and prevent exposure. The ingredients are dried which requires the standard QuEChERS methods [1] to be modified to overcome this difficulty. Gas chromatography is the best technique to separate multicomponents including coextracted interferences, and because the triple quadruple mass spectrometer (GC-MS/MS) is highly sensitive this allows analysis of trace level contamination. In this study, we analyzed over 200 compounds simultaneously using a triple quadrupole gas chromatograph mass spectrometer with the modified QuEChERS method.

Materials and Methods

Pesticides standards, internal standards, quality control standards and a QuEChERS kit were obtained from Restek:

  • GC Multiresidue Pesticide Kit (cat.# 32562)
  • QuEChERS Internal Standard Mix for GC-MS Analysis (cat.# 33267)
  • SV Internal Standard Mix (cat.# 31206)
  • Q-sep QuEChERS Extraction Kit (Original cat.# 23991 discontinued; see cat.# 25848)
 

The total number of targets was 232 compounds (220 pesticides, 6 internal standards, and 6 quality control standards). Ginseng, which can be purchased in any store, was used as a matrix. Using this ginseng, matrix-matched calibration standards (1 to 200 ng/mL) and fortified samples (each two 10 and 50 ng/g) were prepared. Calibration curves were generated by an internal standard method, weighted 1/C and the internal standard was PCB52.

An MRM analytical method was created using the Smart Pesticides Database (Shimadzu). This database has retention indices for all registered compounds, and retention times can be predicted by running an n-alkane sample mixture (AART: Automatic Adjustment of Retention Time). According to estimated retention times, Smart MRM creates an optimum data acquisition time program (Figure 1).

Figure 1: Data Acquisition Time Program Created by Smart MRM

figure-article-FSAR3080-01.jpg

Extraction and Clean-up Procedure

  • Weigh 1.0 ± 0.05 g ground ginseng powder into 50 mL polypropylene centrifuge tube.
  • Add 10 mL HPLC-grade water and vortex the tube vigorously.
  • Add 10 mL of the ACN/IS Extraction Solvent.
  • Allow the tube to sit for 15 min.
  • Add 4 g anhydrous MgSO4 and 1 g NaCl.
  • Shake the tube vigorously on a mechanical shaker for 30 min.
  • Centrifuge the 50 mL tubes at 3000–4500 rpm × 5 min.
  • Condition the GCB/PSA (0.25 g/0.5 g) SPE columns with ~250 mg anhydrous Na2SO4 on top using 3 column volumes of acetone.
  • Insert a collection rack consisting of 15 mL disposable glass centrifuge tube on a SPE vacuum manifold.
  • Add 1.25 mL of the ACN extract.
  • Rinse with 1 mL acetone.
  • Elute with 12 mL of 3:1 v/v acetone:toluene.
  • Evaporate (50 °C) the eluent to ~100 μL gently.
  • Add 500 μL of toluene to the Blank/fortified samples, calibration standard solutions to matrix matched calibration standards.
  • Add 20 μL quality control standards (12.5 μg/mL) and ~50 mg of anhydrous MgSO4 to all samples.
  • Vortex for 5 sec.
  • Centrifuge the tubes at 3000 g × 5 min.
  • Transfer the toluene extract using a Pasteur pipette to ALS GC vials.
 

Result and Discussion

Matrix Matched Calibration

The chromatogram in Figure 2 shows a 10 ng/mL matrix matched calibration standard. Of the 232 compounds, 230 could be detected in ±0.1 min of estimated retention time by AART. The remaining two compounds, 1,4-Dichlorobenzene-d4 and Naphthalene-d8 of six quality control standards, had eluted before 4 min. Although retention times were shifted, they were with identified within about ±0.2 min of estimated.

Figure 2: MRM Chromatogram of 10 ng/mL Matrix Matched Calibration Standard (Internal standards and quality control standards are not displayed.)

GC_FS0568
ColumnRxi-5ms, 30 m, 0.25 mm ID, 0.25 µm (cat.# 13423)
using Rxi guard column 5 m, 0.25 mm ID (cat.# 10029)
with SilTite μ-Union connector kit (cat.# 23885)
Standard/SampleGC Multiresidue pesticide kit (cat.# 32562)
Diluent:Toluene
Conc.:10 ng/mL
Injection
Inj. Vol.:2 µL pulsed splitless
Liner:Topaz 3.5 mm ID single taper inlet liner w/wool (cat.# 23336)
Inj. Temp.:250 °C
Pulse Pressure:36 psi (248.2kPa)
Pulse Time:1.5 min
Oven
Oven Temp.:90 °C (hold 1 min) to 130 °C at 30 °C/min to 330 °C at 10 °C/min (hold 2 min)
Carrier GasHe, constant linear velocity
Linear Velocity:55 cm/sec
DetectorShimadzu GCMS TQ8040
Transfer Line Temp.:290 °C
Analyzer Type:Quadrupole
Source Temp.:230 °C
Electron Energy:70 eV
Ionization Mode:EI
InstrumentShimadzu GCMS-TQ8040
NotesMatrix-matched calibration standards were prepared in ginseng. Calibration curves were generated by the internal standard method using PCB52 as the internal standard. An MRM analytical method was created using the Shimadzu pesticides database.

Although the multiresidue pesticides kit mixes are formulated to ensure maximum long-term stability and reliability as packaged, stability may become an issue when a large number of compounds with different chemical functionalities are combined together into a single mix. This should be taken into consideration for quantitative analysis.


AcknowledgementChromatogram provided by Shimadzu. Publication 3655-11615-10ANS (C146-E334), First Edition, December 2016. Residual Pesticides Analysis of Botanical Ingredients Using Gas Chromatography Triple Quadrupole Mass Spectrometry. Riki Kitano, Tairo Ogura, Nicole Lock, Robert Clifford, Julie Kowalski, Jack Cochran, Dan Li

Calibration curves were generated from matrix matched calibration standards, then back calculation and linearity were evaluated.

Back calculation was performed by calculating the concentration of each calibration point, and if the concentration exceeds ±20% of theoretical value, the calibration point would be interpolated with the nearest two points. Over 93% of the compounds with concentration of 1 ng/mL were within ±20% of theoretical calculations and all compounds of concentration 20 to 200 ng/mL were within ±20% (Figure 3).

Figure 3: Difference Between Back Calculation and Theoretical Concentration

figure-article-FSAR3080-03.jpg

This modified QuEChERS method contains dilution steps, and samples will be diluted by quarter. To quantify 10 ng/g concentration, 2 ng/g or lower calibration point are required. Even at low concentrations, the calibration curves show good linearity (Figure 4) and all coefficients of determination (220 pesticides) were greater than 0.99.

Figure 4: Calibration Curves of Representative Six Compounds

figure-article-FSAR3080-04.jpg

Recovery of Fortified Samples

Each two 10 ng/g and 50 ng/g fortified samples were prepared (10 ng/g-1, 10 ng/g-2, 50 ng/g-1, 50 ng/g-2) and these recovery rates were evaluated from the average of three successive data points for each sample.

Of the compounds, 85% showed good recovery within the range of 70 to 120% on 10 ng/g-1 and 50 ng/g-2. As mentioned previously, fortified samples were diluted to 2.5 ng/mL and 12.5 ng/mL. Since calibration curves showed good linearity at low concentration and modified QuEChERS method suppressed interference, good recovery results were achieved. (Some compounds were not quantified correctly because the matrix for the calibration standards originally contained them. Y-intercept were lifted up and this shift might cause incorrect quantification, especially at low concentration. From the standard addition method, 16 pesticides were detected with more than 10 ng/g in matrix.)

In this study, recovery results were rechecked and combined with qualitative information, the relative ion ratio. Ion ratios between the target and reference were compared to that of the 100 ng/g standard and evaluated according to SANCO/12571/2013 [2]). This mentions that the use of relative ratio ±30% as a criterion is recommended.

Table I shows recovery and relative ion ratio for all compounds and Figure 5 shows the combination map of recovery and relative ion ratio, which was generated from this table. Of the compounds, 76% in the 10 ng/g-1 were within ±30% on relative ion ratio with good recovery of between 70 to 120%. For 50 ng/g-2, 83% of the compounds were within a ±30% relative ion ratio. And here, compounds which showed poor recovery and/or over ±30% relative ion ratio were examined.

Table I: Recovery and Relative Ion Ratio; Relative ion ratios were calculated by those of 100 ng/mL standard solution.

ID Compound Name Transitions Recovery
(Average of n = 3)
Relative Ion Ratio
(Average of n = 3)
Target CE Reference CE 10 ng/g-1 10 ng/g-2 50 ng/g-1 50 ng/g-2 10 ng/g-1 10 ng/g-2 50 ng/g-1 50 ng/g-2
1 2,3,5,6-Tetrachloroaniline 228.9 > 158.0 18 230.9 > 158.0 22 72.5 67.0 61.4 68.8 93.6 97.2 98.9 101.1
2 2,4'-Methoxychlor 227.1 > 121.1 16 228.1 > 122.1 16 83.0 101.1 86.5 80.2 94.7 105.0 104.6 106.7
3 2-Phenylphenol 170.1 > 141.1 24 170.1 > 115.1 28 72.7 72.3 63.2 69.0 113.1 112.9 99.1 102.1
4 3,4-Dichloroaniline 161.0 > 99.0 22 161.0 > 126.0 14 74.5 66.2 56.4 64.4 103.8 105.5 105.8 106.0
5 4,4'-Dichlorobenzophenone 139.0 > 111.0 14 139.0 > 75.0 26 77.4 83.2 73.5 73.8 97.5 104.7 102.0 100.3
6 4,4'-methoxychlor olefin 308.0 > 238.1 16 310.0 > 238.1 20 84.4 94.8 85.7 83.0 99.4 101.0 100.0 98.4
7 Acequinocyl deg. 342.2 > 188.1 14 342.2 > 160.1 22 105.3 269.8 201.1 115.2 61.2 62.8 90.7 64.0
8 Acetochlor 223.1 > 132.1 22 223.1 > 147.1 10 77.5 88.3 77.4 77.1 109.0 104.1 102.8 106.2
9 Acrinathrin 289.1 > 93.0 14 181.1 > 152.1 26 102.5 121.4 91.0 82.4 87.0 94.7 92.3 95.1
10 Alachlor 188.1 > 160.1 10 188.1 > 132.1 18 74.1 87.2 77.8 74.1 114.7 107.2 97.3 103.5
11 Aldrin 262.9 > 191.0 34 262.9 > 193.0 28 86.0 66.9 65.2 74.3 79.8 101.1 104.6 93.2
12 Allidochlor 132.1 > 56.0 8 132.1 > 49.0 24 71.8 64.5 59.0 65.9 123.7 118.4 113.4 117.2
13 Anthraquinone 208.1 > 180.1 10 208.1 > 152.1 22 0.0 126.7 47.4 48.0 97.0 83.6 90.4 94.0
14 Atrazine 200.1 > 104.1 18 200.1 > 122.1 8 77.8 94.0 83.3 78.6 105.3 110.1   92.5 100.6
15 Azinphos-ethyl 160.1 > 132.1 4 160.1 > 77.0 18 91.4 115.5 94.5 86.5 102.1 94.8 100.0 98.7
16 Azinphos-methyl 160.1 > 132.1 6 160.1 > 77.0 20 84.1 124.7 93.0 83.3 89.6 103.3 98.2 100.0
17 Benfluralin 292.1 > 264.0 8 292.1 > 160.0 22 78.4 77.0 64.5 70.7 97.7 89.1 96.8 95.3
18 BHC, alpha- 180.9 > 144.9 16 218.9 > 182.9 8 62.5 50.4 58.2 66.1 99.0 104.0 99.2 104.3
19 BHC, beta- 180.9 > 144.9 16 218.9 > 182.9 8 69.6 87.6 76.8 71.8 102.2 102.9 98.9 104.1
20 BHC, delta- 180.9 > 144.9 16 218.9 > 182.9 8 28.6 87.6 69.0 67.8 102.5 104.3 106.4 104.2
21 BHC, gamma- 180.9 > 144.9 16 218.9 > 182.9 8 64.1 73.3 62.0 69.8 94.8 93.9 103.1 102.8
22 Bifenthrin 181.1 > 166.1 12 181.1 > 179.1 12 84.6 99.2 89.3 81.4 97.0 104.4 116.7 105.9
23 Bioallethrin 123.1 > 81.1 10 136.1 > 93.1 14 81.7 100.7 83.6 71.9 463.4 563.8 200.4 228.1
24 Biphenyl 154.1 > 128.1 22 154.1 > 115.1 24 90.0 67.9 56.2 65.1 105.5 105.1 106.3 106.0
25 Bromfenvinfos-methyl 294.9 > 109.0 16 296.9 > 109.0 16 85.5 98.5 84.2 77.6 103.5 92.2 100.9 102.7
26 Bromfenvinphos 266.9 > 159.0 14 268.9 > 161.0 16 78. 97.8 88.2 79.2 102.1 94.7 100.9 102.3
27 Bromophos 330.9 > 315.9 14 328.9 > 313.9 18 70.9 86.2 77.2 76.4 104.6 98.6 97.2 98.6
28 Bromophos-ethyl 358.9 > 302.9 16 302.9 > 284.9 18 78.0 86.9 76.5 75.8 91.9 89.6 98.5 98.4
29 Bromopropylate 340.9 > 182.9 18 340.9 > 184.9 20 85.8 104.5 94.3 85.6 101.4 100.9 101.0 99.2
30 Bupirimate 273.1 > 108.1 16 273.1 > 193.1 8 94.4 102.8 92.2 87.0 82.0 98.3 98.1 92.8
31 Captafol 79.0 > 77.0 14 79.0 > 51.0 20 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.
32 Captan 149.1 > 105.1 4 149.1 > 79.1 14 90.7 95.3 83.4 75.3 232.6 240.2 118.7 135.5
33 Carbophenothion 341.9 > 157.0 14 341.9 > 199.0 8 81.9 97.6 84.2 79.2 58.6 66.3 80.4 91.6
34 Carfentrazone-ethyl 340.1 > 312.1 14 312.1 > 151.1 24 85.3 100.6 94.0 87.3 81.5 81.8 101.9 94.7
35 Chlorbenside 125.0 > 99.0 18 127.0 > 89.0 18 80.3 83.4 73.5 71.8 86.9 93.5 96.8 99.3
36 Chlordane, cis- 374.8 > 265.9 26 372.8 > 265.9 22 76.4 84.2 76.6 77.1 94.8 99.2 105.3 101.1
37 Chlordane, trans- 374.8 > 265.9 26 372.8 > 265.9 22 76.6 77.3 75.9 72.9 96.3 106.5 103.2 102.7
38 Chlorfenapyr 247.1 > 227.0 16 247.1 > 200.0 24 84.3 114.9 87.1 85.0 51.3 71.3 112.2 98.6
39 Chlorfenson 175.0 > 111.0 12 301.9 > 175.0 8 77.0 89.1 81.4 76.4 99.5 100.6 100.5 98.0
40 Chlorfenvinphos, (E)- 323.0 > 267.0 16 267.0 > 159.0 18 110.3 114.8 74.7 72.9 270.4 484.8 103.9 99.9
41 Chlorfenvinphos, (Z)- 323.0 > 267.0 16 267.0 > 159.0 18 85.5 96.6 82.7 78.5 105.8 101.5 104.8 101.2
42 Chlorobenzilate 251.0 > 139.0 14 139.0 > 75.0 26 87.5 106.9 88.9 80.3 98.3 92.0 100.1 101.1
43 Chloroneb 206.0 > 141.0 20 193.0 > 113.0 18 65.4 59.8 59.8 68.6 111.1 110.8 107.9 105.9
44 Chlorothalonil 263.9 > 168.0 24 263.9 > 228.8 18 N.D. N.D. 5.2 N.D. N.D. N.D. 82.3 N.D.
45 Chlorpropham 213.1 > 171.1 6 127.1 > 92.0 18 77.7 81.7 72.5 73.3 99.6 101.7 99.0 101.4
46 Chlorpyrifos 313.9 > 257.9 14 313.9 > 285.9 8 71.2 77.8 74.9 74.2 100.5 93.8 93.6 95.7
47 Chlorpyrifos-methyl 285.9 > 93.0 22 287.9 > 93.0 22 77.0 89.3 73.1 75.3 92.9 91.7 102.6 98.0
48 Chlorthal-dimethyl 298.9 > 220.9 24 300.9 > 222.9 26 78.8 81.9 77.3 73.7 90.7 95.7 96.1 99.9
49 Chlorthiophos-1 256.9 > 239.0 14 256.9 > 193.0 22 91.4 108.5 84.2 83.5 8.4 49.4 77.2 68.6
50 Chlorthiophos-2 324.9 > 268.9 14 268.9 > 205.0 18 76.1 96.8 84.6 80.0 73.8 79.3 95.8 101.5
51 Chlorthiophos-3 324.9 > 268.9 14 268.9 > 205.0 18 78.4 100.2 86.8 77.8 92.6 85.9 100.8 97.8
52 Chlozolinate 258.9 > 188.0 14 330.9 > 258.9 6 75.6 82.2 75.9 76.1 91.7 98.3 103.8 104.3
53 Clomazone 204.1 > 107.0 20 204.1 > 78.0 26 72.7 72.2 70.9 74.9 100.7 99.6 101.8 98.6
54 Coumaphos 362.0 > 109.0 16 362.0 > 226.0 14 90.1 110.4 98.2 89.7 84.4 84.7 94.5 94.9
55 Cycloate 154.2 > 72.0 6 215.1 > 154.2 4 69.8 66.7 61.2 69.5 89.3 89.9 93.3 94.0
56 Cyfluthrin-1 226.1 > 206.1 14 163.1 > 127.1 6 92.8 111.7 98.2 92.1 105.2 118.8 100.9 96.1
57 Cyfluthrin-2 226.1 > 206.1 14 163.1 > 127.1 6 92.5 113.1 91.9 90.2 124.6 121.5 105.1 97.6
58 Cyfluthrin-3 226.1 > 206.1 14 163.1 > 127.1 6 81.4 96.8 92.5 81.7 117.8 160.7 124.5 128.0
59 Cyfluthrin-4 226.1 > 206.1 14 163.1 > 127.1 6 76.5 95.7 106.8 88.7 167.1 159.4 121.8 126.4
60 Cyhalothrin, lambda- 208.1 > 181.1 8 197.1 > 141.0 12 88.4 108.0 92.1 85.5 99.2 113.2 99.5 96.9
61 Cypermethrin-1 163.1 > 127.1 6 163.1 > 109.1 22 96.0 113.8 94.6 89.9 108.8 93.7 117.4 111.3
62 Cypermethrin-2 163.1 > 127.1 6 163.1 > 109.1 22 89.6 119.7 98.0 88.7 99.2 113.1 94.8 100.1
63 Cypermethrin-3 163.1 > 127.1 6 163.1 > 109.1 22 75.9 124.9 103.1 96.9 126.1 114.1 96.6 104.1
64 Cypermethrin-4 163.1 > 127.1 6 163.1 > 109.1 22 76.6 100.1 84.6 81.5 115.3 119.9 124.9 120.1
65 Cyprodinil 224.1 > 197.1 22 224.1 > 131.1 14 82.0 88.9 80.0 71.2 138.1 117.5 100.5 112.6
66 DDD, o,p'- 235.0 > 165.0 24 235.0 > 199.0 16 83.6 96.0 79.8 75.3 87.0 86.6 100.1 99.1
67 DDD, p,p'- 235.0 > 165.0 24 235.0 > 199.0 16 80.2 94.6 83.6 78.2 104.4 98.8 102.6 104.3
68 DDE, o,p'- 246.0 > 176.0 30 248.0 > 176.0 28 73.7 83.1 75.7 71.7 101.7 97.9 99.0 100.3
69 DDE, p,p'- 246.0 > 176.0 30 317.9 > 248.0 24 76.9 99.7 76.2 73.5 101.1 93.8 98.8 98.3
70 DDT, o,p'- 235.0 > 165.0 24 235.0 > 199.0 16 79.0 89.1 78.0 74.3 93.9 97.6 100.1 101.2
71 DDT, p,p'- 235.0 > 165.0 24 235.0 > 199.0 16 75.2 95.1 80.7 75.8 96.8 95.0 102.9 97.7
72 Deltamethrin 252.9 > 93.0 20 252.9 > 171.9 8 83.8 109.4 92.2 85.3 99.9 99.3 102.5 99.7
73 Di-allate-1 234.1 > 150.0 20 234.1 > 192.1 14 75.3 66.5 63.3 70.7 93.8 93.0 100.9 103.3
74 Di-allate-2 234.1 > 150.0 20 234.1 > 192.1 14 72.4 65.1 63.0 70.5 88.9 107.7 100.0 94.1
75 Diazinon 304.1 > 179.1 10 304.1 > 162.1 8 76.4 70.3 69.5 74.4 62.3 80.6 97.9 86.4
76 Dichlobenil 170.9 > 100.0 24 170.9 > 136.0 14 71.2 65.3 58.2 65.4 96.5 97.4 96.5 98.2
77 Dichlofluanid 223.9 > 123.1 8 223.9 > 77.0 28 65.0 71.1 57.8 56.9 75.4 87.4 94.4 101.7
78 Dicloran 206.0 > 176.0 10 206.0 > 124.0 24 78.1 76.6 69.7 77.0 79.0 87.7 100.6 91.0
79 Dieldrin 276.9 > 241.0 8 262.9 > 193.0 34 80.2 80.3 89.0 85.0 154.2 185.9 102.7 91.4
80 Dimethachlor 197.1 > 148.1 10 199.1 > 148.1 10 78.4 90.6 77.9 76.8 99.6 89.1 100.2 101.6
81 Diphenamid 239.1 > 167.1 8 239.1 > 72.0 16 94.7 96.0 88.3 79.8 126.1 123.6 112.2 115.5
82 Diphenylamine 169.1 > 66.0 24 169.1 > 77.0 28 78.2 74.6 65.6 71.1 85.3 99.9 98.3 100.6
83 Disulfoton 186.0 > 153.0 6 186.0 > 97.0 16 71.4 66.2 64.6 78.9 142.4 124.1 107.9 85.8
84 Edifenphos 173.0 > 109.0 10 310.0 > 173.0 14 82.6 103.7 91.0 83.6 97.9 94.6 100.3 98.2
85 Endosulfan ether 240.9 > 205.9 16 238.9 > 203.9 16 62.7 64.4 67.2 69.5 126.7 95.3 104.8 101.2
86 Endosulfan sulfate 271.8 > 236.9 18 386.8 > 252.9 16 83.8 88.4 87.0 85.1 42.5 55.6 83.3 85.8
87 Endosulfan, alpha- 194.9 > 160.0 8 194.9 > 125.0 24 74.0 80.0 75.6 80.7 77.6 76.9 92.3 83.4
88 Endosulfan, beta- 194.9 > 160.0 8 194.9 > 125.0 24 83.1 99.4 81.6 81.7 102.1 67.3 93.2 100.2
89 Endrin 262.9 > 193.0 28 262.9 > 228.0 22 84.1 89.9 77.2 75.3 50.2 49.4 85.3 88.2
90 Endrin aldehyde 249.8 > 214.9 26 344.9 > 244.9 16 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.
91 Endrin ketone 316.9 > 244.9 20 314.9 > 242.9 18 73.4 91.5 84.1 88.0 108.9 95.4 107.6 101.9
92 EPN 169.1 > 140.9 8 169.1 > 77.0 22 90.3 107.4 89.2 82.3 94.3 102.9 100.2 98.8
93 Ethalfluralin 276.0 > 202.0 18 316.1 > 276.0 10 73.3 67.7 63.0 67.1 95.2 96.4 100.9 100.6
94 Ethion 230.9 > 129.0 24 230.9 > 174.9 14 81.4 97.1 84.2 77.9 118.3 108.6 101.8 102.6
95 Etofenprox 163.1 > 135.1 10 163.1 > 107.1 18 87.1 101.1 95.6 87.3 97.4 103.1 98.8 97.8
96 Etridiazole 210.9 > 182.9 10 210.9 > 139.9 22 70.0 60.1 58.0 66.9 88.2 102.0 102.0 100.4
97 Fenamiphos 303.1 > 195.1 8 288.1 > 260.1 6 88.7 104.6 99.3 87.1 120.9 106.0 96.8 100.1
98 Fenarimol 251.0 > 139.0 14 330.0 > 139.0 8 83.9 106.7 96.5 89.4 97.4 92.6 99.3 96.0
99 Fenchlorphos 284.9 > 269.9 16 286.9 > 271.9 18 80.5 81.4 71.5 74.8 89.8 83.8 99.1 97.2
100 Fenitrothion 277.0 > 260.0 6 260.0 > 125.1 12 78.0 89.3 79.3 75.8 104.9 99.2 111.4 109.6
101 Fenpropathrin 265.1 > 210.1 12 265.1 > 89.0 28 90.3 102.8 96.8 88.2 68.9 75.9 90.9 94.4
102 Fenson 141.0 > 77.0 16 267.9 > 141.0 6 78.3 88.0 77.9 74.5 91.3 92.7 100.8 96.8
103 Fenthion 278.0 > 169.0 14 278.0 > 125.0 20 80.4 81.9 78.2 76.0 93.9 96.0 102.2 104.1
104 Fenvalerate-1 225.1 > 147.1 10 419.1 > 225.1 6 82.2 100.7 94.6 88.9 95.5 92.4 103.2 99.3
105 Fenvalerate-2 225.1 > 147.1 10 419.1 > 225.1 6 75.7 106.7 93.1 86.5 73.5 70.0 86.2 89.7
106 Fipronil 366.9 > 212.9 30 368.9 > 214.9 30 92.8 113.2 99.5 82.8 93.8 96.2 88.0 96.7
107 Fluazifop-P-butyl 282.1 > 91.0 18 383.1 > 282.1 14 77.4 94.0 89.0 80.6 101.9 96.4 99.6 100.5
108 Fluchloralin 306.0 > 264.0 8 326.0 > 63.0 16 76.4 78.4 76.9 75.1 95.8 96.0 90.4 96.5
109 Flucythrinate-1 157.1 > 107.1 12 199.1 > 107.1 22 86.9 111.9 95.6 87.3 119.8 120.4 107.1 105.2
110 Flucythrinate-2 157.1 > 107.1 12 199.1 > 107.1 22 89.4 111.0 96.0 86.6 105.1 108.4 102.6 104.6
111 Fludioxonil 248.0 > 127.0 26 248.0 > 154.0 20 94.1 110.3 96.5 86.1 91.9 101.1 98.1 96.0
112 Fluquinconazole 340.0 > 298.0 20 340.0 > 313.0 14 85.2 107.0 98.9 88.9 97.7 98.5 101.4 101.1
113 Fluridone 328.1 > 259.0 24 328.1 > 127.0 24 91.5 117.7 100.3 91.4 80.1 77.3 93.4 95.7
114 Flusilazole 233.1 > 165.1 14 233.1 > 152.1 14 78.1 93.3 84.9 83.2 105.9 91.5 94.8 95.4
115 Flutolanil 173.0 > 95.0 26 281.1 > 173.0 12 84.1 108.0 93.4 84.7 104.1 101.1 100.0 99.8
116 Flutriafol 219.1 > 123.1 14 219.1 > 95.0 28 82.9 109.6 89.8 84.2 120.1 115.2 103.9 103.9
117 Fluvalinate-1, tau- 250.1 > 55.0 18 250.1 > 200.1 16 86.7 112.8 91.9 85.5 79.4 79.9 90.8 90.4
118 Fluvalinate-2, tau- 250.1 > 55.0 18 250.1 > 200.1 16 90.4 112.0 89.1 83.9 89.6 95.5 102.5 104.7
119 Folpet 259.9 > 130.0 14 261.9 > 130.0 18 65.2 82.9 72.8 67.0 97.2 89.1 99.1 98.3
120 Fonofos 246.0 > 137.1 6 246.0 > 109.1 18 76.6 74.7 65.8 71.4 106.8 97.6 102.1 101.2
121 Heptachlor 271.8 > 236.9 20 273.8 > 238.9 16 68.6 65.4 65.0 68.6 92.3 102.0 104.0 101.2
122 Heptachlor-exo-epoxide 352.8 > 262.9 14 352.8 > 316.9 10 81.1 80.4 71.8 79.1 33.7 39.0 88.6 71.5
123 Hexachlorobenzene 283.8 > 248.8 24 283.8 > 213.8 28 45.7 28.8 48.1 62.3 101.4 100.7 102.7 99.3
124 Hexazinone 171.1 > 71.0 16 171.1 > 85.0 16 93.2 112.9 96.1 88.2 105.3 101.3 104.0 105.2
125 Iodofenphos 376.9 > 361.8 22 376.9 > 331.8 32 80.0 86.8 75.8 74.2 83.8 102.3 97.3 97.1
126 Iprodione 314.0 > 245.0 12 314.0 > 56.0 22 110.5 156.0 102.0 89.9 91.0 99.9 102.2 107.0
127 Isazofos 257.0 > 162.0 8 257.0 > 119.0 18 80.0 87.4 74.4 74.7 109.5 107.1 96.0 102.6
128 Isodrin 192.9 > 157.0 20 262.9 > 192.9 28 76.4 73.7 67.4 71.2 88.2 99.0 110.1 98.6
129 Isopropalin 280.1 > 238.1 8 280.1 > 133.1 18 76.5 88.1 73.6 71.4 89.8 82.7 97.9 106.1
130 Lenacil 153.1 > 136.1 14 153.1 > 82.1 16 85.1 103.2 97.5 85.7 109.0 108.9 124.1 111.8
131 Leptophos 376.9 > 361.9 24 374.9 > 359.9 24 86.8 102.6 89.0 82.6 95.4 99.8 101.9 103.0
132 Linuron 248.0 > 61.0 16 250.0 > 61.0 16 68.3 84.7 77.7 77.9 98.3 83.1 105.8 108.6
133 Malathion 173.1 > 99.0 14 158.1 > 125.0 10 79.9 87.3 77.6 75.3 95.2 97.4 101.3 100.9
134 Metalaxyl 249.2 > 190.1 8 249.2 > 146.1 22 83.5 88.7 89.5 81.1 103.0 122.4 104.0 100.7
135 Metazachlor 209.1 > 132.1 18 211.1 > 132.1 20 83.3 93.2 83.8 80.1 97.8 100.1 101.6 104.8
136 Methacrifos 208.0 > 180.0 8 240.0 > 208.0 4 75.6 68.7 62.9 67.2 93.3 89.0 95.3 101.8
137 Methoxychlor 227.1 > 169.1 24 227.1 > 212.1 14 82.8 101.8 90.8 83.5 109.0 108.5 103.5 103.2
138 Metolachlor 238.1 > 162.1 12 238.1 > 133.1 26 77.0 89.0 77.9 75.4 104.8 96.6 101.4 102.3
139 Mevinphos-1 192.0 > 127.0 12 127.0 > 95.0 18 75.7 70.7 64.1 71.4 95.8 104.8 103.6 102.2
140 MGK 264-1 164.1 > 93.0 10 164.1 > 80.0 24 112.8 102.9 86.2 81.3 92.5 104.4 108.1 104.7
141 MGK 264-2 164.1 > 98.0 12 164.1 > 67.0 8 74.8 89.7 79.3 78.2 116.0 100.8 93.7 96.0
142 Mirex 271.8 > 236.8 18 273.8 > 238.8 18 71.4 80.4 73.6 71.2 99.9 97.3 100.7 99.6
143 Myclobutanil 179.1 > 125.0 14 179.1 > 152.0 8 83.7 104.4 90.8 84.1 122.4 127.5 112.5 108.8
144 N-(2,4-dimethylphenyl) formamide 149.1 > 106.1 16 149.1 > 121.1 6 86.6 88.5 73.0 71.4 334.2 367.6 157.5 169.6
145 Nitralin 316.1 > 274.0 8 274.0 > 169.0 12 101.1 116.0 95.4 87.2 98.7 104.0 106.2 97.4
146 Nitrofen 202.0 > 139.0 24 282.9 > 253.0 12 83.4 91.9 85.9 77.0 89.0 95.2 99.6 104.3
147 Nonachlor, cis- 406.8 > 299.9 24 406.8 > 334.9 16 80.0 91.3 79.8 77.0 59.7 48.5 84.3 87.0
148 Nonachlor, trans- 406.8 > 299.9 24 406.8 > 334.9 16 74.8 86.0 80.8 78.2 58.4 72.4 82.3 84.6
149 Norflurazon 303.0 > 145.0 22 145.0 > 95.0 18 94.7 111.0 98.7 85.0 92.7 95.4 99.2 100.8
150 Oxadiazon 258.0 > 175.0 8 302.0 > 175.0 14 78.8 88.7 84.7 76.9 95.1 101.4 100.4 103.2
151 Oxyfluorfen 361.0 > 300.0 14 361.0 > 317.0 6 101.4 106.2 90.9 80.4 91.2 97.7 101.4 102.1
152 Paclobutrazol 236.1 > 125.0 14 236.1 > 167.0 10 92.2 116.7 92.8 86.1 98.0 86.2 100.9 100.1
153 Parathion 291.1 > 137.0 6 291.1 > 81.0 24 99.8 96.8 80.7 76.0 100.1 115.2 104.9 108.1
154 Parathion-methyl 263.0 > 109.0 14 263.0 > 246.0 6 85.5 91.6 74.2 77.4 71.7 69.8 96.2 93.7
155 Pebulate 161.1 > 128.1 6 128.1 > 57.0 6 64.1 59.1 56.9 66.7 115.3 111.1 101.3 101.7
156 Penconazole 248.1 > 157.1 26 159.1 > 123.1 22 90.9 92.6 75.3 75.4 90.0 94.4 97.6 97.5
157 Pendimethalin 252.1 > 162.1 10 252.1 > 191.1 8 84.0 84.2 73.9 73.8 89.5 98.9 102.2 104.0
158 Pentachloroaniline 262.9 > 191.9 22 264.9 > 193.9 18 23.6 83.6 52.0 72.4 99.4 99.0 101.1 98.8
159 Pentachloroanisole 279.9 > 236.8 26 279.9 > 264.8 12 69.0 65.8 60.2 67.9 102.8 93.3 101.7 101.4
160 Pentachlorobenzene 249.9 > 214.9 18 249.9 > 176.9 26 59.9 27.0 47.6 62.0 104.3 113.2 108.4 104.3
161 Pentachlorobenzonitrile 274.8 > 239.8 18 272.8 > 202.9 30 69.3 65.6 63.2 68.7 90.1 88.2 96.3 95.7
162 Pentachlorothioanisole 295.8 > 262.9 14 295.8 > 245.8 30 55.8 75.7 62.7 69.7 92.4 96.3 94.9 93.5
163 Permethrine, cis- 183.1 > 153.1 14 183.1 > 168.1 14 86.6 112.1 96.8 87.5 101.7 108.3 99.5 100.2
164 Permethrine, trans- 183.1 > 153.1 14 183.1 > 168.1 14 96.0 131.5 97.0 88.4 100.4 98.3 103.6 102.4
165 Perthane 223.2 > 167.1 14 223.2 > 193.1 28 85.3 92.7 81.9 78.1 97.1 106.8 102.3 100.3
166 Phenothrin-1 183.1 > 153.1 14 183.1 > 168.1 14 N.D. N.D. N.D. 84.8 N.D. N.D. 111.5 92.4
167 Phenothrin-2 183.1 > 153.1 14 183.1 > 168.1 14 100.7 113.7 95.7 86.7 101.4 112.1 105.1 100.1
168 Phorate 260.0 > 75.0 8 231.0 > 129.0 24 74.3 63.8 61.9 69.7 92.7 116.3 99.8 101.6
169 Phosalone 182.0 > 102.0 14 182.0 > 111.0 14 86.3 101.6 93.9 84.4 117.0 123.8 101.2 104.5
170 Phosmet 160.0 > 77.0 24 160.0 > 105.0 18 86.7 105.4 92.6 83.0 100.8 100.1 103.5 101.2
171 Piperonyl butoxide 176.1 > 131.1 12 176.1 > 117.1 20 84.1 112.8 92.1 85.9 104.9 118.6 102.2 102.3
172 Pirimiphos ethyl 304.1 > 168.1 12 318.1 > 166.1 12 78.1 94.3 79.1 73.8 83.5 84.4 97.4 105.8
173 Pirimiphos-methyl 290.1 > 125.0 22 290.1 > 233.1 12 80.4 88.9 78.5 76.1 93.3 92.5 101.2 99.4
174 Pretilachlor 262.1 > 202.1 10 238.1 > 162.1 10 77.0 95.2 86.0 79.7 109.6 79.5 93.4 102.5
175 Prochloraz 180.1 > 138.1 12 180.1 > 69.0 20 68.1 110.1 85.4 81.5 106.2 102.1 91.1 91.2
176 Procymidone 283.0 > 96.0 10 285.0 > 96.0 10 12.4 140.1 78.8 79.4 103.0 101.7 104.7 101.8
177 Prodiamine 321.1 > 279.1 6 321.1 > 203.1 10 86.1 94.7 81.6 78.3 88.5 88.3 93.6 99.0
178 Profenofos 338.9 > 268.9 18 336.9 > 266.9 14 87.1 93.5 90.0 85.6 107.6 107.6 93.3 91.1
179 Profluralin 318.1 > 199.1 16 318.1 > 55.0 22 66.3 64.9 65.7 74.8 105.2 95.9 97.6 91.7
180 Propachlor 176.1 > 57.0 8 176.1 > 77.0 24 74.9 76.4 67.3 71.4 114.9 106.5 103.8 102.7
181 Propanil 217.0 > 161.0 10 160.9 > 126.0 18 93.5 105.3 91.4 78.7 100.7 106.9 95.8 104.6
182 Propargite 173.1 > 135.1 16 173.1 > 107.1 24 88.0 98.7 90.8 85.5 120.0 122.8 74.1 66.1
183 Propisochlor 223.1 > 132.1 20 223.1 > 147.1 8 83.7 90.8 79.4 77.9 91.0 100.1 98.4 101.0
184 Propyzamide 172.9 > 109.0 26 172.9 > 74.0 28 83.0 91.4 77.1 76.5 98.7 100.0 108.7 106.3
185 Prothiofos 266.9 > 238.9 10 309.0 > 238.9 14 74.3 88.9 78.0 73.9 102.4 94.4 102.7 101.2
186 Pyraclofos 194.0 > 138.0 22 360.1 > 194.0 14 91.6 111.4 97.0 87.0 84.1 89.9 99.3 100.1
187 Pyrazophos 221.1 > 193.1 12 221.1 > 149.1 14 88.7 111.9 97.3 86.1 101.7 96.0 99.9 103.7
188 Pyridaben 147.1 > 117.1 22 147.1 > 132.1 14 87.5 106.4 92.5 84.1 99.2 105.1 102.0 102.5
189 Pyridaphenthion 340.0 > 199.1 8 199.1 > 92.0 16 100.2 120.0 95.0 89.3 114.1 129.2 109.5 107.5
190 Pyrimethanil 198.1 > 118.1 28 198.1 > 158.1 18 74.4 82.5 75.3 73.2 95.2 99.1 96.4 98.5
191 Pyriproxyfen 136.1 > 96.0 14 226.1 > 186.1 14 81.3 91.9 92.8 84.4 59.7 78.1 88.1 84.8
192 Quinalphos 146.1 > 118.0 10 146.1 > 91.0 24 71.7 86.6 79.6 72.9 204.6 155.7 122.4 117.8
193 Quintozene 294.8 > 236.8 16 264.8 > 236.8 10 61.7 0.0 18.5 71.1 100.1 100.7 101.5 100.3
194 Resmethrin-1 171.1 > 128.1 12 171.1 > 143.1 6 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.
195 Resmethrin-2 171.1 > 143.1 6 171.1 > 128.1 14 85.8 96.4 85.8 78.1 86.0 97.9 95.6 100.0
196 Sulfotep 322.0 > 294.0 4 322.0 > 202.0 10 79.1 71.8 65.5 71.8 94.6 98.9 98.0 95.0
197 Sulprofos 322.0 > 156.0 8 156.0 > 108.0 28 80.7 97.3 86.0 83.2 101.1 95.9 97.3 95.1
198 Tebuconazole 250.1 > 125.1 22 250.1 > 153.1 12 76.8 82.9 68.1 71.6 112.5 96.6 98.9 98.1
199 Tebufenpyrad 333.1 > 171.1 20 333.1 > 276.1 8 87.7 105.2 96.7 84.7 97.6 97.3 94.6 95.6
200 Tecnazene 260.9 > 202.9 14 202.9 > 85.0 24 78.8 59.9 59.7 72.4 93.9 99.1 96.8 95.8
201 Tefluthrin 177.0 > 127.1 16 177.0 > 137.1 16 79.0 81.2 67.5 72.5 92.6 94.9 101.0 98.3
202 Terbacil 161.0 > 88.0 20 117.0 > 76.0 8 97.5 111.6 86.5 82.0 81.8 77.9 92.5 96.1
203 Terbufos 231.0 > 128.9 26 231.0 > 174.9 14 78.8 80.6 65.2 70.3 111.6 100.1 102.8 104.7
204 Terbuthylazine 229.1 > 173.1 6 214.1 > 71.0 16 94.9 91.0 77.6 77.1 82.6 91.6 99.7 103.3
205 Tetrachlorvinphos 328.9 > 109.0 20 330.9 > 109.0 22 87.4 102.5 87.3 81.0 96.0 93.6 99.9 96.6
206 Tetradifon 355.9 > 159.0 18 355.9 > 228.9 12 84.1 96.6 93.6 88.5 87.9 103.1 102.9 96.7
207 Tetramethrin-1 164.1 > 107.1 14 164.1 > 77.0 22 N.D. N.D. 100.5 94.8 N.D. N.D. 106.5 114.1
208 Tetramethrin-2 164.1 > 107.1 14 164.1 > 77.0 22 103.2 129.6 98.4 88.4 115.2 117.0 107.9 113.8
209 THPI 151.1 > 79.0 18 151.1 > 77.0 28 79.4 85.0 81.5 78.2 104.7 104.1 103.6 108.0
210 Tolclofos-methyl 264.9 > 93.0 24 264.9 > 219.9 22 72.8 78.6 72.6 73.8 98.8 100.9 102.3 103.6
211 Tolylfluanid 238.0 > 137.1 14 181.1 > 138.1 10 66.8 79.8 65.9 64.1 118.7 117.3 114.3 107.4
212 Transfluthrin 163.1 > 127.1 6 163.1 > 143.1 16 84.2 85.7 77.1 77.6 106.3 115.0 97.7 99.0
213 Triadimefon 208.1 > 111.0 22 208.1 > 127.0 14 88.4 98.2 86.7 80.5 99.5 103.9 97.9 104.7
214 Triadimenol 168.1 > 70.0 10 128.1 > 65.0 22 N.D. N.D. 101.2 94.2 N.D. N.D. 80.9 85.6
215 Tri-allate 268.1 > 184.0 20 270.1 > 186.0 20 80.0 75.6 68.6 74.6 102.4 85.9 94.6 98.1
216 Triazophos 257.0 > 162.0 8 257.0 > 134.0 22 89.7 112.4 94.8 86.4 95.9 80.8 90.3 88.2
217 Tricyclazole 189.0 > 161.9 12 189.0 > 135.0 18 91.5 95.7 84.5 81.8 105.9 118.7 105.2 97.3
218 Triflumizole 278.1 > 73.0 6 206.1 > 186.1 8 87.2 88.2 71.5 76.8 83.2 110.9 97.0 99.2
219 Trifluralin 306.1 > 264.1 8 306.1 > 160.1 22 79.9 73.6 64.4 72.5 92.7 100.3 100.8 101.1
220 Vinclozolin 285.0 > 212.0 12 212.0 > 172.0 16 86.3 92.8 79.9 80.7 84.3 96.4 104.2 103.3
QC-1 1,4-Dichlorobenzene-d4 150.0 > 78.0 24 115.1 > 78.0 12
QC-2 Acenaphthene-d10 164.0 > 160.0 30 164.0 > 134.0 38
QC-3 Chrysene-d12 240.0 > 236.0 30 240.0 > 212.0 24
QC-4 Naphthalene-d8 136.0 > 84.0 22 136.0 > 82.0 28
QC-5 Perylene-d12 264.0 > 263.0 34 264.0 > 262.0 24
QC-6 Phenanthrene-d10 188.0 > 160.0 24 187.0 > 159.0 18
IS-1 2,2',5-Trichlorobiphenyl 255.9 > 186.0 26 257.9 > 186.0 26
IS-2 2,4,4'-Trichlorobiphenyl 255.9 > 186.0 26 257.9 > 186.0 26
IS-3 2,2',5,5'-Tetrachlorobiphenyl 257.0 > 222.0 12 292.0 > 220.0 26
IS-4 Triphenylmethane 244.1 > 167.1 16 244.1 > 165.1 26
IS-5 Triphenylphosphate 215.1 > 168.1 16 325.1 > 169.1 20
IS-6 Tris(1,3-dichloroisopropyl)phosphate 379.0 > 159.0 12 381.0 > 159.0 12

Compounds outside the red box (Figure 5) were classified to four groups.

Figure 5: Combination Map Between Recovery and Ion Ratio (Average of n = 3 for Each Fortified Sample) Red box shows the area of 70–120% recovery and ±30% relative ion ratio.

figure-article-FSAR3080-05.jpg

Group A showed low recovery; this group consisted mainly of compounds which have a low boiling point. They may have been lost in the evaporation step. Group B showed high relative ion ratios and this was caused by interference from matrix. Group C showed high recovery; this group consisted of 10 ng/g fortified sample. Some of these were in matrix originally and quantified incorrectly. Others caused by their transitions which had low response and low stability. Group D showed low relative ion ratio. It was necessary to set higher response transitions. By modifying some procedures and parameters, positions of these compounds may improve.

Conclusion

This study shows that the modified QuEChERS method combined with GC-MS/MS achieved consistent pesticides monitoring in botanical ingredients.

Although dried sample could make a heavy and difficult matrix, the modified QuEChERS method, SPE column cleanup, and toluene dilution steps suppressed interference from matrix. The GC-MS/MS detected very low amounts of pesticides even though the sample was diluted. This analytical method takes only 30 minutes in total run time and covers over 200 pesticides. It provides a high throughput solution in laboratories doing this type of analysis.

References

[1] M. Anastassiades, S. J. Lehotay, D. Štajnbaher, F. J. Schenck, Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and “Dispersive Solid-Phase Extraction” for the Determination of Pesticide Residues in Produce, J. AOAC Int., 86 (2003) 412–431
[2] European Commission, Health & Consumer Protection Directorate-General, Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed, SANCO/12571/2013

FSAR3080-UNV

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