Abstract
An effective electroanalytical method was developed for the quantitative evaluation of fenitrothion pesticide. The electrochemically modified carbon paste electrode CPE was constructed by applying a safranine layer on its surface. Safranine monomer is easily oxidized. So, a safranine layer was applied via electropolymerization using cyclic voltammetry in (2 × 10(-5) M) safranine buffered solution with phosphate buffer BPS at pH.6, potential window (- 1.6: + 2 V), scan rate 100 mV/s. The morphology of the modified electrode was characterized using SEM images. The electropolymerization process was characterized by observing the gradual increases of the peak current with the subsequent scanning cycles. This modified CPE electrode showed an obvious sensitivity by cyclic voltammetry towards the cathodic peak of the fenitrothion nitro group at approximately - 0.73V with good sensitivity by enhancing it to be approximately 10 times more sensitive than on a bare carbon paste electrode CPE. The number of cycles was optimized for the electropolymerization process to be 12 cycles. Where, the peak current at - 0.73 V was gradually enhanced until 12 cycles when it is obviously decreased before slightly increasing again. The reproducibility of the modified electrode was ensured by repeating the sweep cycles using LSV for determining the fenitrothion at 5 µM where it was found that the peak current was unchanged for 10 sweeps before it starts to drop gradually. LSV voltammetry at previously optimized conditions of the potential window (- 0.4: - 1 V), sweep rate 100 mV/s, phosphate buffer at pH.6 was used for the quantitative studies. Where, the pHs of the determining medium were varied from pH 5.5 to pH 8 using phosphate buffer. It was observed that the most identified peak current was at pH.6 which is then decreased gradually until it completely disappeared at pH 8. The optimal accumulation time by adsorption of 140 s for the fenitrothion pesticide was confirmed in the range of (20 s-170 s). Where, the peak current was increased gradually with time up to 140 s then a plateau with a constant response was observed. The developed method showed an excellent linearity range of (1 μM:15 μM) with R(2) parameter equal to 0.99906. LOD and LOQ were calculated to be 0.1 μM, and 0.34 μM respectively. Satisfactory levels have been reached for the calculated recovery, accuracy. Precision limits not exceed 1% for both repeatability and reproducibility measurements. F-value and t-value were measured for the suggested LSV method versus the standard HPLC method for the concentration of 8 μM fenitrothion and were found to be 1.482 and 0.123, respectively which didn't exceed the tabulated values. The ruggedness of the suggested method was examined toward deliberate safranine concentration variations in the concentration range of (0.01 mM-0.03 mM). Insignificant differences for the mean recovery at (98.33-98.93%) and precision at (1.39-2.6%) were observed. Hence, the reliability and validity of the developed LSV method were achieved and it was considered as rigid method.