GC-TQMS application: Quantitative analysis of residual agricultural chemicals in food by GC-MS/MS - Quantitative analysis of pesticides in carrot extract -

  • Summary

MSTips No.260

As "food safety" is recognized as an increasingly important issue on a global scale, many nations have their own regulations on residual agricultural chemicals in food. In Japan, the positive list system, which was enforced at the end of May 2006, stipulates a uniform standard of 10 ppb as a quantity that is considered safe for human health. Under the positive list system, more agricultural chemicals need to be examined, and as a result, techniques capable of accurately and collectively analyzing residual agricultural chemicals in food are in increasing demand. While mass spectrometry (MS) is known for its high detection sensitivity, MS/MS is becoming the mainstream of pesticide analysis for its superior sensitivity and selectivity.
The JMS-TQ4000GC, JEOL’s latest GC-MS/MS, has a unique ion storage/ejection mechanism within the MS/MS collision cell and incorporates new firmware to support MS/MS analysis with up to 36,000 transitions. In this work, we performed quantitative analysis of residual agricultural chemicals in carrot extract using a JMS-TQ4000GC.

Measuring Conditions

A pesticide standard solution from FUJIFILM Wako Pure Chemical Corporation (PL series) was used that consisted of equal amounts of PL 1, 2, 3, 4, 5, 6, 11, and 12. Afterwards, the solution was diluted to 1, 5, 10, 50 and 100 ppb. PEG 300 was used to protect the pesticides from thermal decomposition in the GC injection liner.
For the sample, 15 g of carrots was processed by using the AOAC 2007.01 extraction method, and the resulting extraction solution was mixed with 100 ppb of the standard solution at 9:1. The sample was quantitatively analyzed for 150 pesticides. Table 1 shows the measurement conditions used for the analysis.

GC-MS/MS, JMS-TQ4000GC

GC-MS/MS, JMS-TQ4000GC

Table1 Measuring Conditions

[GC-TQMS condition]

System JMS-TQ4000GC (JEOL)
Ionization mode EI+: 70eV, 50µA
GC column VF-5ms, 30m × 0.25mm, 0.25µm
Oven temp. 50°C (1min) → 25°C/min → 125°C → 10°C/min → 300°C
Inlet temperature 250°C
Inlet mode Splitless, 2µL
He flow 1.0mL/min (Constant Flow)
MS/MS mode Peak Dependent SRM

Results

Figure 1 top row shows the data acquired from the original carrot extract while the bottom row shows the data from the carrot extraction solution with the pesticides added. MS/MS, with its high mass selectivity, detected agricultural chemicals without being affected by contaminants in the carrot extract. Table 2 shows the quantitative results of 150 pesticides (n=5) and their reproducibility (CV). For most agricultural chemicals, the recovery rate was 70 to 120% and the CV was 10% or less, demonstrating the effectiveness of the JMS-TQ4000GC for pesticide analysis.

Fig.1 SRM chromatograms, upper: Carrot extract solution only, lower: 10ppb pesticides in the carrot extract solution

Figure 1. SRM chromatograms
Top row: Carrot extract solution only; bottom row: 10 ppb pesticides in carrot extract solution

Table 2. Quantitative results of 150 pesticides in carrot extract solution (n=5)

No. Compound min Quantitative value (ppb) Ave. (ppb) CV(%)
No.1 No.2 No.3 No.4 No.5

1

Atrazine

12.37 9.1 10.1 9.6 9.8 9.1 9.5 4.5

2

Benthiocarb

14.68 10.7 10.9 11.8 11.2 10.9 11.1 4.0

3

cis-Permethrin

20.68 11.0 10.8 11.5 11.2 11.0 11.1 2.5
4 Diflufenican 18.31 9.7 8.7 10.6 9.9 9.3 9.7 7.3
5 Fenamiphos 16.24 8.9 8.2 9.4 9.0 9.4 9.0 5.6
6 Fenarimol 20.20 10.2 10.2 10.1 10.5 10.4 10.3 1.6
7 Fenpropimorph 14.74 10.9 11.0 11.1 11.8 10.8 11.1 3.5
8 Norflurazon 17.94 9.5 9.5 9.5 10.2 10.0 9.7 3.3
9 Oxadiazon 16.50 9.5 9.2 10.4 9.6 9.8 9.7 4.8
10 Penconazole 15.45 10.8 10.6 11.0 11.0 10.8 10.8 1.6
11 Pendimethalin 15.29 11.5 11.4 11.3 11.4 13.1 11.7 6.7
12 Procymidone 15.70 10.9 10.5 9.1 12.1 9.7 10.5 10.7
13 Spiroxamine 1 13.78 9.7 9.9 10.2 10.8 10.5 10.2 4.3
14 Spiroxamine 2 14.31 10.0 9.3 10.2 10.1 10.2 10.0 4.0
15 Tefluthrine 12.92 10.6 10.1 10.8 11.6 10.5 10.7 5.4
16 Terbufos 12.63 8.3 8.0 8.7 9.2 8.4 8.5 5.3
17 Terbutryn 14.31 10.0 9.7 10.5 10.4 10.4 10.2 3.6
18 trans-Permethrin 20.68 11.0 10.8 11.5 11.2 11.0 11.1 2.5
19 Alachlor 13.84 9.1 9.0 9.9 10.1 9.3 9.5 5.2
20 Buprofezin 16.68 12.0 9.8 10.5 11.5 11.8 11.1 8.5
21 cis-Chlorfenvinphos 15.49 8.2 7.8 9.1 8.8 8.8 8.6 5.9
22 Cyproconazole 1 17.03 9.3 10.0 10.8 9.8 8.4 9.7 9.1
23 Cyproconazole 2 17.03 11.3 10.2 10.2 11.8 12.6 11.2 9.3
24 Difenoconazole 1 23.10 10.5 10.4 10.5 10.5 10.4 10.5 0.7
25 Difenoconazole 2 23.18 10.6 10.5 10.5 10.6 10.6 10.6 0.5
26 Ethion 17.34 9.1 8.4 9.7 8.9 8.7 9.0 5.6
27 Fenitrothion 14.33 7.9 6.9 7.3 7.4 6.6 7.2 7.2
28 Fenthion 14.73 9.3 7.9 8.5 9.1 8.2 8.6 7.2
29 Fluridone 22.18 11.2 11.4 11.5 11.5 10.1 11.2 5.5
30 Hexazinone 18.24 8.3 8.0 9.1 8.9 8.8 8.6 4.8
31 Isofenphos oxon 14.79 9.3 9.3 10.1 10.4 9.2 9.7 5.6
32 Isophenphos 15.43 9.8 9.6 10.3 9.5 9.9 9.8 3.0
33 Isoprothiolane 16.44 10.2 9.9 10.9 10.2 9.6 10.2 4.4
34 Propargite 1 18.31 7.7 7.4 8.8 8.1 8.1 8.0 6.8
35 Propargite 2 18.31 8.4 7.8 9.1 8.7 8.4 8.5 6.0
36 Propiconazole 1 17.93 11.5 10.4 10.8 11.5 10.8 11.0 4.5
37 Propiconazole 2 18.07 11.8 11.3 11.2 11.1 10.7 11.2 3.5
38 Propyzamide 12.73 10.6 9.8 10.6 10.9 10.5 10.5 3.9
39 Pyriproxyfen 19.72 10.0 10.4 10.7 10.4 9.7 10.2 3.8
40 trans-Chlorfenvinphos 15.25 10.6 9.5 10.2 10.6 10.5 10.3 4.3
41 Triadimenol 1 15.7 10.2 7.7 9.6 9.9 8.7 9.2 11.1
42 Triadimenol 2 15.84 10.7 9.4 9.9 10.3 9.8 10.0 4.7
43 Triallate 13.13 7.5 7.3 7.6 8.1 7.6 7.6 3.5
44 Vinclozoline 13.76 8.1 8.2 8.1 9.2 8.6 8.4 5.6
45 Acetamiprid 18.92 10.8 8.7 9.6 9.3 10.3 9.7 8.6
46 Allethrin 1 15.43 12.0 9.6 11.6 11.1 11.8 11.2 8.5
47 Allethrin 2 15.51 6.4 6.6 7.3 7.5 7.3 7.0 7.1
48 Bitertanol 1 20.66 12.1 12.1 12.5 12.3 12.2 12.3 1.2
49 Bitertanol 2 20.76 9.6 9.6 10.3 10.0 10.0 9.9 3.1
50 Bromopropylate 19.00 8.7 8.3 9.1 9.3 9.2 8.9 4.4
51 Chlorobenzilate 17.19 7.8 7.0 8.2 7.9 7.6 7.7 5.5
52 Chlorpyrifos 14.63 8.5 8.2 8.9 9.9 9.9 9.1 8.6
53 Oxyfluorfen 16.59 11.6 11.1 9.1 9.5 11.2 10.5 10.7
54 Parathion 14.80 9.1 8.8 7.5 7.8 8.7 8.4 8.0
55 Pirimiphos methyl 14.24 9.3 9.2 9.6 10.0 9.7 9.6 3.5
56 Propanil 13.67 9.8 9.2 9.8 10.0 10.6 9.9 5.0
57 Pyridaben 20.87 10.4 9.8 10.9 10.5 9.9 10.3 4.5
58 Quinoxyfen 18.00 11.2 10.7 11.4 11.5 11.0 11.2 2.8
59 Simazine 12.29 9.3 9.8 9.7 9.8 8.7 9.5 4.9
60 Tebuconazole 18.38 10.8 10.2 9.4 10.9 10.1 10.3 5.9
61 Triadimefon 14.87 10.4 12.5 11.5 11.1 11.0 11.3 7.0
62 Triazophos 17.65 7.7 7.3 7.6 7.2 7.0 7.3 3.7
63 Ametryn 14.00 9.7 9.9 10.2 9.9 9.8 9.9 1.6
64 Azaconazole 16.83 12.4 12.4 12.8 13.3 12.8 12.7 3.1
65 Bupirimate 16.66 10.5 10.6 11.1 11.5 11.8 11.1 5.0
66 Butachlor 16.01 9.5 9.4 9.7 9.6 9.9 9.6 1.8
67 Chlorthal dimethyl 14.73 9.0 8.5 9.3 9.0 9.6 9.1 4.6
68 Dicloran 12.19 8.0 7.7 9.2 8.7 8.4 8.4 7.3
69 Diethofencarb 14.63 10.6 10.5 11.1 10.7 10.6 10.7 2.2
70 Dimepiperate 15.74 12.0 12.2 13.3 11.3 11.7 12.1 6.2
71 Dimethenamid 13.61 10.9 10.9 11.2 11.1 10.8 11.0 1.4
72 Etoxazole 19.03 10.7 9.2 10.8 10.6 9.5 10.2 7.3
73 Fluacrypyrim 17.38 9.8 9.6 10.2 10.3 10.5 10.1 3.7
74 Lenacil 18.14 11.4 11.4 11.5 11.3 11.5 11.4 0.6
75 Pyriminobac methyl 1 17.96 12.3 12.0 11.4 11.8 12.0 11.9 2.7
76 Pyriminobac methyl 2 12.88 10.6 10.5 10.0 11.0 10.6 10.5 3.5
77 Pyroquilon 19.53 9.6 10.2 10.0 10.9 9.8 10.1 4.8
78 Tetradifon 13.87 7.1 7.3 8.6 8.4 7.8 7.8 8.1
79 Tolclofos-methyl 16.61 9.7 8.8 10.3 9.7 10.2 9.7 5.8
80 Uniconazole P 13.66 9.7 9.9 10.5 10.5 10.1 10.2 3.7
81 Acetochlor 17.83 9.5 11.7 12.1 11.9 10.3 11.1 10.3
82 Benalaxyl 13.57 9.2 9.2 10.4 9.4 8.5 9.3 7.3
83 Benfuresate 11.71 10.2 9.1 9.9 9.8 9.3 9.6 4.6
84 Cadusafos 11.37 8.1 9.0 8.9 9.4 8.9 8.9 5.7
85 Chlorpropham 15.61 9.2 8.7 8.9 9.4 9.0 9.0 3.1
86 Diclocymet 1 15.91 10.3 10.6 10.5 10.6 9.7 10.3 3.6
87 Diclocymet 2 15.40 10.0 9.4 9.3 10.2 9.8 9.7 3.7
88 Dimethametryn 14.49 11.3 11.4 11.5 11.2 10.9 11.3 2.0
89 Esprocarb 21.83 9.2 9.3 9.8 9.3 8.9 9.3 3.3
90 Etofenprox 16.08 11.5 11.8 11.7 11.5 11.5 11.6 1.0
91 Fenothiocarb 13.27 10.7 10.2 10.3 10.3 10.5 10.4 1.8
92 Iprobenfos 16.92 9.2 9.3 9.8 9.8 9.6 9.5 2.6
93 Isoxathion 17.61 6.9 6.0 7.5 7.4 7.0 7.0 8.4
94 Mepronil 14.04 10.7 10.2 10.3 10.0 10.4 10.3 2.5
95 Prometryn 10.85 10.1 9.6 10.3 10.4 9.7 10.0 3.6
96 Propachlor 16.41 9.6 8.6 9.1 9.9 9.2 9.3 5.4
97 Prothiofos 15.99 8.4 9.0 9.1 9.3 7.4 8.6 8.7
98 Pyrifenox 1 12.89 10.9 10.2 10.1 9.8 9.1 10.0 6.5
99 Pyrimethanil 13.94 9.6 10.1 9.8 9.9 9.1 9.7 3.9
100 Simetryn 13.06 10.8 10.0 11.3 10.8 10.3 10.6 4.9
101 Terbacil 14.82 12.4 12.6 13.3 12.5 13.1 12.8 3.0
102 Tetraconazole 18.31 12.0 12.6 11.3 12.3 10.8 11.8 6.3
103 Thenylchlor 16.58 7.7 8.3 8.8 8.4 8.2 8.3 4.9
104 Tribufos 16.66 8.8 8.4 8.7 9.0 9.1 8.8 2.9
105 Tricyclazole 15.72 7.5 6.9 9.4 9.0 8.4 8.2 12.3
106 Zoxamide (decomposed) 13.40 10.2 9.8 10.5 9.5 10.2 10.0 3.7
107 Benoxacor 14.44 8.1 7.9 8.5 7.9 7.4 8.0 4.8
108 Bromacil 13.70 9.3 7.3 10.1 8.6 8.7 8.8 11.4
109 Bromobutide 16.17 11.2 15.3 14.0 12.5 12.6 13.1 11.9
110 Butamifos 13.56 10.1 10.0 11.0 10.5 10.1 10.3 4.1
111 Dichlofenthion 15.12 10.1 10.0 10.2 10.5 9.8 10.1 2.6
112 Diphenamid 16.42 12.3 11.6 11.9 12.1 11.6 11.9 2.7
113 Hexaconazole 14.00 10.3 10.3 10.5 10.3 10.4 10.4 1.0
114 Mefenoxam 16.33 9.3 10.2 10.0 9.3 9.8 9.7 4.3
115 Napropamide 17.40 10.1 9.6 9.4 10.3 10.1 9.9 3.7
116 Oxadixyl 16.07 10.5 10.3 10.5 10.5 10.2 10.4 1.3
117 Paclobutrazol 19.31 11.5 10.7 10.9 10.6 11.3 11.0 3.5
118 Phenothrin 1 19.42 11.3 12.7 12.6 11.9 12.9 12.2 5.5
119 Phenothrin 2 18.98 10.2 10.4 10.7 10.7 10.5 10.5 2.0
120 Piperophos 12.94 9.1 9.2 9.5 10.2 9.2 9.4 4.9
121 Prohydrojasmon 1 13.23 8.6 8.2 8.9 9.3 8.9 8.8 4.8
122 Prohydrojasmon 2 12.42 12.7 9.9 10.5 8.5 9.2 10.2 15.7
123 Propazine 18.63 10.1 10.2 10.2 10.0 9.7 10.0 2.0
124 Pyributicarb 15.51 12.1 11.5 11.7 11.9 11.8 11.8 1.9
125 Pyrifenox 2 15.63 10.4 9.9 9.8 10.1 9.6 10.0 3.1
126 Quinalphos 19.16 10.5 10.0 10.7 10.6 10.0 10.3 3.4
127 Tebufenpyrad 24.05 9.0 9.8 10.0 9.8 9.3 9.6 4.1
128 Tolfenpyrad 14.78 9.3 9.6 9.4 9.7 9.3 9.5 1.7
129 Aldrin 16.26 7.6 7.6 7.4 8.0 7.5 7.6 3.2
130 cis-Chlordane 14.97 8.4 7.1 9.1 9.2 7.9 8.3 10.3
131 Dicofol 16.78 11.9 10.8 11.5 11.3 11.1 11.3 3.6
132 Dieldrin 17.19 10.6 9.4 10.7 11.0 9.7 10.3 6.8
133 Endrin 14.07 11.3 11.4 9.8 9.2 11.2 10.6 9.7
134 Heptachlor 16.02 7.3 6.9 8.0 8.3 7.1 7.5 7.9
135 trans-Chlordane 14.40 9.2 10.1 9.9 9.7 9.8 9.7 3.5
136 1-Naphthylacetamide 15.87 11.6 10.1 10.7 10.1 10.7 10.6 5.7
137 Bromophos ethyl 16.80 8.8 7.7 9.5 8.9 8.7 8.7 7.6
138 Carboxin 15.98 11.4 10.9 11.3 11.5 11.1 11.2 2.3
139 Chlorbenside 16.42 9.2 9.6 9.4 9.1 9.3 9.3 2.0
140 Chlorofenson 24.99 7.8 7.4 8.4 8.3 8.2 8.0 5.1
141 clomazone 12.47 8.8 8.9 8.8 8.9 8.6 8.8 1.2
142 Disulfoton 12.98 8.7 8.6 9.3 10.2 8.7 9.1 7.3
143 Epoxiconazole 18.61 10.6 10.4 10.8 10.7 10.6 10.6 1.6
144 Ethofumesate 14.37 9.8 10.1 10.1 10.2 10.4 10.1 2.3
145 Fenamidone 19.17 10.3 10.4 10.3 10.2 9.7 10.2 2.7
146 Flutriafol 16.28 10.5 11.1 10.6 10.6 10.3 10.6 2.9
147 Isazophos 12.96 9.0 9.1 9.7 10.2 9.2 9.4 5.2
148 Phorate 11.79 7.0 7.8 7.6 8.3 7.8 7.7 5.8
149 Picolinafen 18.97 11.1 11.0 11.1 11.4 10.8 11.1 2.2
150 Propaphos 15.89 11.0 10.8 11.4 10.5 10.7 10.9 3.0
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