Application Note # CA 284781 Screening for Pyrethroid Insecticides in Sediment Samples by GC/MS/MS

Abstract
A simple screening method for Pyrethroid insecticides in sediment samples is described. Electron impact ionization (EI) with tandem MS/MS in combination with programmed temperature vaporization injection (PTV) were used in order to obtain excellent specificity and low limits of detection.

Experimental

451-GC Gas Chromatographic Conditions

Column: Carrier: Injector: Injector Conditions: Column Temperature Program: BR-5ms, 30 m x 0.25 mm x 0.25 um He 1.0 mL/min PTV with 3.4 mm ID Siltek Fritted Liner, 8 uL injection 60 C hold 0.4 min to 310 C at 200 C/min, hold 30 min 55 C, hold 3 min, ramp to 200 at 40 C/min, hold 1 min; ramp to 310 C at 5 C/min, hold 1 min.

Introduction
Pyrethroids are synthetic chemical insecticides whose chemical structures were adapted from the chemical structures of the pyrethrins. Pyrethroids have been modified to increase their stability in sunlight. They are toxic to aquatic organisms at extremely low concentrations, especially to invertebrates that are at the bottom of the food chain (1). Many of the compounds end up in wastewater outfalls due to ineffective water treatment. As a result, state and federal agencies have initiated monitoring programs to characterize the extent of contamination in water supplies and their potential impact on aquatic life. In general, there are no set requirements for minimum detection or reporting levels. However, the lowest reporting level that can be achieved by a given technique is desired. The Scion TQ triple quadrupole mass spectrometer in EI mode with PTV injection is ideal for screening sediment extracts at low to sub-part-per-billion concentrations.

Scion TQ MS Conditions
Ion Source Temperature: Transferline Temperature: Filament Delay time: Filament Emission Current: Dwell Time: 250 C 280 C 12 min 80 uA 100 ms each transition

Table 1: MS/MS Parameters for Pyretroids Insecticides Compound Name Lambda Cyhalothrin_Ep1+2 Fenvalerate+Esfenvalerate RT (min) 19.150 19.150 24.230 24.230 24.230 Bifenthrin 17.560 17.560 17.560 trans+cis-Permethrin 20.880 20.880 20.880 Cypermethrin-Isomers Cyfluthrin-Isomers Resmethrin_1+2 Fenpropathrin Deltamethrin-1+2 22.580 22.580 21.980 21.980 16.690 16.690 17.860 17.860 25.200 25.200 RT Window 1.000 1.000 1.000 1.000 1.000 0.500 0.500 0.500 1.000 1.000 1.000 1.200 1.200 1.200 1.200 1.000 1.000 0.500 0.500 1.000 1.000 Precursor 208 181 167 225 225 181 181 181 183 183 183 181 181 226 206 171 171 265 265 253 253 Product 181 152 125 91 119 165 166 115 168 128 152 152 127 206 151 128 143 181 210 174 172 Collision Energy -10 -20 -15 -25 -10 -18 -10 -40 -18 -20 -20 -20 -30 -15 -15 -12 -12 -20 -10 -10 -10

Calibration standards in hexane were prepared at 0.1, 1, 5, 10, 25, 50, 100, and 200 ppb. In addition, a blank sediment matrix was spiked at concentrations of 0.5, 5, 10, 25, 50, 100, and 200 ppb.

Figure 1: Optimized scan information for each compound is downloaded directly from the factory installed library. Bifenthrin MRM transitions are shown here.

Sample preparation: 5 g copper powder/magnesium sulfate was added to 20 g wet sediment. The mixture was extracted with 2 x 75ml 50:50 acetone:hexane using a shaker at 185 rpm (2 x15 minutes). The extracts were concentrated to a final volume of 2 mL and cleaned up on Florisil Sep Pak.

Bifenthrin

Results
The Scion TQ has a unique software feature known as Compound Based Scanning (CBS) that was used to easily set up the MRMs required for the analysis. The pyrethroids were found in the Factory Library within the CBS software, and were directly downloaded into the scan acquisition method. (Figure 1). In addition, the data handling table is automatically created and linked to the scan acquisition method. This saves time because the operator does not have to create additional tables and manage changes to the analytical method. The use of MS/MS provided excellent sensitivity and specificity for the analysis. Compounds detected in the sediment sample spiked at 0.5 ppb are shown in Figure 2. Calibration curves prepared in pure solvent (hexane) and in blank sediment extracts were linear indicating no matrix interference from the sediment extract. An example calibration curve is shown in Figure 3.
Lambda-cyhalothrin Epimres 1 and 2

Conclusion
PTV injection combined with the sensitivity and specificity of MS/MS result in excellent low-level screening of pyrethroids in river and lake sediments. The Scion TQ with Compound Based Scanning allows easy set-up and management of the pyrethroid MRM parameters. Compound MRM information is loaded directly into the method by choosing them from a factory or user created library. It links the mass spectrometer acquisition table directly with data handling parameters, streamlining the data process.
Cyuthrin isomers

Figure 2: MS/MS for Bifenthrin (top), two epimers of lamda-cyhalothrin (mid), and cyfluthrin isomers (bottom) in the sediment matrix

Figure 3: Calibration curves for Bifenthrin prepared in hexane from 0.1 to 200 ppb (plot at left) and those prepared in a spiked sediment extract (plot at right) calibrated from 0.5 ppb to 200 ppb.

Acknowledgements
California Department of Food and Agriculture

References
1 http://www.beyondpesticides.org/pesticides/factsheets/Synthetic%20Pyrethroids.pdf

Author:
Ed George Keywords Scion TQ GC/MS/MS Sediment Samples Environmental Testing Instrumentation & Software Scion TQ 451-GC 436-GC 8400 A/S

For research use only. Not for use in diagnostic procedures.

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