Page 49 - Application Handbook - Liquid Chromatography

Application No.L497
News

Table 1 Analytical Conditions
[SFE] [SFC]
Solvent : A) Super critical fluid of CO2 Column : Shim-pack UC-RP (250 mm L. × 4.6 mm I.D., 5 μm)
B) 0.1 % Ammmonium formate in methanol Mobile Phase : A) Super critical fluid of CO2
Flowrate : 5 mL/min B) 0.1 % Ammmonium formate in methanol
Extraction : 0-3 min. Static mode (B.Conc. 5 %) Time Program : B.Conc. 0 % (0 min.) → 10 % (11 min.) → 30% (14 min.) →
3-6 min. Dynamic mode (B.Conc. 5 %) 40 % (14.01-17 min.)
Extraction Flowrate : 3 mL/min
Vessel Temp. : 40 °C Make-up : 0.1 % Ammmonium formate in methanol (0.1 mL/min.)
BPR Pressure : A) 14.8 MPa, B) 15 MPa (split rate: 3 %) Column Temp. : 40 °C
Make-up : 0.1 % Ammmonium formate in methanol (0.4 mL/min.) BPR Pressure : A) 15 MPa, B) 40 MPa
Detector : LCMS-8050 MRM mode
n Analysis of Standard Mixture of Pesticides
The standard mixture sample of 510 pesticide components
were mixed with a dehydrating agent and analyzed using Ethofenprox Hexa umuron Benzofenap Mepronil
2 ng/g
1 ng/g
1 ng/g
1 ng/g
the analytical conditions indicated in Table 1. Fig. 3 shows 1250 60000 35000
12500 30000
the results. Using the system, we were able to accomplish 1000 50000
10000 40000 25000
the entire process, from extraction to data acquisition, in 7500 750 20000
about 45 minutes per analysis. For 327 components, we 5000 500 30000 15000
obtained good repeatability for the concentration range 2500 250 20000 10000
10000
from 1 to 100 ng/g (less than 30 %RSD for relative 5000
0 0 0 0
standard deviation for peak area at respective 12.0 13.0 13.0 14.0 12.0 13.0 13.0 14.0
concentrations) and good linearity (contribution ratio of at Prometyn Fenamidone Ethylchlozate Imazosulfuron
least R = 0.99). Table 2 also shows how pesticides with a 1 ng/g 50000 2 ng/g 40000 1 ng/g 1 ng/g
2
wide range of polarities were analyzed with good 20000 40000 35000 10000
repeatability and linearity. 15000 30000
30000 25000 7500
10000 20000
20000 5000
15000
5000 10000 10000 2500
5000
0 0 0
11.0 12.0 14.0 15.0 13.0 14.0 15.0 16.0
Bensulfuron methyl Primisulfuron methyl Halosulfuron methyl Azimsulfuron
1 ng/g 1 ng/g 1 ng/g 1 ng/g
125000
25000 30000 40000
100000
20000 25000
75000 20000 30000
15000
15000 20000
50000
10000
10000
25000 5000 5000 10000
0 0 0 0
13.0 14.0 13.0 14.0 13.0 14.0 13.0 14.0
Fig. 4 MRM Chromatograms of Representative Pesticides
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 min n Analysis of a Tomato
Fig. 3 Mass Chromatogram of Standard Pesticide Mixture Solution Analysis of 10 ng/g of 510 pesticide components added
to a tomato resulted in good repeatability (less than
Table 2 Repeatability and Linearity for Representative Pesticides 20 %RSD for the relative standard deviation of the peak
Compounds LogPow Repeatability Range R 2 area) and a good recovery rate (70 to 120 %) for 248
(%RSD, n=5) (ng/g) components. Plots of LogPow and recovery rate results
Ethofenprox 6.9 6.1 1-100 0.9991 are shown in Fig. 5. It shows that pesticides with a wide
Hexaflumuron 5.68 6.8 1-100 0.9992 range of polarities were analyzed with good recovery.
Benzofenap 4.69 1.4 2-200 0.9990
Mepronil 3.66 4.6 1-100 0.9993
Prometryn 3.34 2.7 1-100 0.9994
Fenamidone 2.8 3.0 2-200 0.9991
Ethylchlozate 2.5 3.0 1-100 0.9996
Imazosulfuron 1.6 6.2 1-100 0.9998
Bensulfuron methyl 0.79 8.1 1-100 0.9996
Primisulfuron methyl 0.2 5.5 1-100 0.9994
Halosulfuron methyl -0.02 5.5 1-100 0.9996
Azimsulfuron -1.4 4.2 1-100 0.9998
<Acknowledgments> Fig. 5 LogPow vs. Recovery Rate for Tomato Analysis
This Application News bulletin includes results obtained in cooperation with Osaka University, Kobe University, and the Miyazaki Agricultural Research
Institute from the program for the "Development of Systems and Technology for Advanced Measurement and Analysis," sponsored by the Japan
Science and Technology Agency (JST). We are deeply grateful to all those involved.
First Edition: Oct. 2015

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