Analysis of Pesticides (II) Metribuzin & their metabolites in Rice Jun Yonekubo, Nihon Waters, JAPAN

Transcription

1 Waters Alliance LC/MS System Analytical Conditions Chromatograms Mass Spectra Calibration Quantitation Analysis of Pesticides (II) Metribuzin & their metabolites in Rice Jun Yonekubo,, JAPAN Key Words Pesticides, sensitivity, calibration, electrospray 1

2 Analytical Conditions Waters Alliance 269 HPLC Pump Conditions Column Symmetry C18, 3.5 um, 2.1 x 15 mm.3 AcOH aq. 75. ACN 18. MeOH 7. Flow (ml/min).3 Run Time (mins) 15. Column Temperature ( C) 4. Waters ZMD MS Detector Conditions MS Ion Energy: 3.5 Volts LM Resolution: 1.7 HM Resolution: 1.7 Multiplier: 65 Volts Pressures Analyser Vacuum: 2.6e-5 mbar Gas Flow: 3.4 lit/hr Ionization mode: ES/APcI+ Function type: Scan Mass range: 15 to 25 Cone Voltage: 35 Ionization mode: ES/APcI- Function type: Scan Mass range: 15 to 25 Cone Voltage: 35 2

3 Metribuzin and their 3 metabolites (5ppm) standard mixture mix, 5ppm 144 (5.287) 185. DK:MW=184 1: Scan ES+ 4.53e5 3: Diode Array e (6.442) : Scan ES- 1.31e5 DADK:MW=169 1: Scan ES+ 1.13e (9.27) 2. 1: Scan ES+ 6.38e5 DA:MW= (12.511) : Scan ES+ 7.97e5 2: Scan ES- 4.44e Metribuzin:MW= m/z Time 3

4 ESI (left) and APcI (right) detection of 5ppm std.mixture : Diode Array e3 3: Diode Array e ESI positive : Scan ES+ 1.17e6 APcI positive : Scan AP+ 4.3e ESI negative : Scan ES- 4.71e5 2: Scan AP ; e APcI negative Time Time 4

5 ESI (left) and APcI (right) detection of.5ppm standard mixture 5_Metribuzin mix ESI 1: SIR of 1 Channel ES e : SIR of 1 Channel AP e4 APcI 5_Metribuzin mix : SIR of 1 Channel ES e : SIR of 1 Channel AP e6 5_Metribuzin mix : SIR of 1 Channel ES e : SIR of 1 Channel AP e5 5_Metribuzin mix 4: SIR of 1 Channel ES e6 4: SIR of 1 Channel AP e Time Time 5

6 1ppb standard mixture (left) and Spiked Rice Sample (right) 1_Metribuzin mix : SIR of 1 Channel ES e4 1_spike : SIR of 1 Channel ES e4 5 1_Metribuzin mix : SIR of 1 Channel ES e4 1_spike : SIR of 1 Channel ES e4 12 1_Metribuzin mix : SIR of 1 Channel ES e4 12 1_spike : SIR of 1 Channel ES e4 2 1_Metribuzin mix 4: SIR of 1 Channel ES e5 3 1_spike 4: SIR of 1 Channel ES e Time Time 6

7 Compound 1 name: DK Coefficient of Determination: Calibration curve: * x + Response type: External Std, Curve type: Linear, Origin: Force, Weighting: Null, Axis trans: None 9.76e5 Response Conc Compound 2 name: DADK Coefficient of Determination: Calibration curve: * x + Response type: External Std, Curve type: Linear, Origin: Force, Weighting: Null, Axis trans: None 8.75e5 Response Conc

8 Compound 3 name: DA Coefficient of Determination:.999 Calibration curve: e6 * x + Response type: External Std, Curve type: Linear, Origin: Force, Weighting: Null, Axis trans: None 1.98e6 Response Conc Compound 4 name: Metribuzin Coefficient of Determination: Calibration curve: e6 * x + Response type: External Std, Curve type: Linear, Origin: Force, Weighting: Null, Axis trans: None 5.25e6 Response Conc

9 Quantify Compound Summary Report (I ) Compound 1: DK Name Type Std Conc* RT Conc.* BS/Conc.* 1_Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard Control Analyte _spike Analyte _spike Analyte Compound 2: DADK Name Type Std Conc* RT Conc.* BS/Conc.* 1_Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard Control Analyte _spike Analyte _spike Analyte * ppm 9

10 Quantify Compound Summary Report (II ) Compound 3: DA Name Type Std Conc* RT Conc.* BS/Conc.* 1_Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard Control Analyte _spike Analyte _spike Analyte Compound 4: Metribuzin Name Type Std Conc* RT Conc.* BS/Conc.* 1_Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard _Metribuzin mix Standard Control Analyte _spike Analyte _spike Analyte * ppm 1