ABSTRACT
We developed an ultra-performance liquid chromatography-tandem mass spectral method to determine the fungicide carboxin and its metabolites, oxycarboxin and carboxin sulfoxide in peanut samples. The method was used to detect the concentration of the analytes in the samples from fields and markets. The total residue quantities in peanut kernels were used to evaluate the chronic dietary risk of total carboxin upon peanut consumption. The estimated dietary intake of carboxin from peanuts whose seeds had been treated with carboxin at the recommended dose was between 0.020% and 0.344% of acceptable daily intake and the risk was found to be negligible. The chronic dietary risk assessment from markets and commercial field samples for various groups of humans indicated that the group with the greatest degree of exposure was 45 to 75-year-old women who lived in rural areas. However, their acceptable daily intake percentage was 0.006%, meaning that their health risk was extremely small.
Subject(s)
Arachis/chemistry , Carboxin/analysis , Dietary Exposure/analysis , Food Contamination/analysis , Adolescent , Adult , Aged , Carboxin/analogs & derivatives , Carboxin/metabolism , Child , Child, Preschool , China , Chromatography, High Pressure Liquid/methods , Dietary Exposure/adverse effects , Female , Fungicides, Industrial/analysis , Fungicides, Industrial/metabolism , Humans , Male , Middle Aged , No-Observed-Adverse-Effect Level , Risk Assessment , Rural Population , Seeds/drug effects , Sulfoxides/analysisABSTRACT
A new direct laser photo-induced fluorescence high performance liquid chromatography (DL-PIF-HPLC) method is developed for the simultaneous determination of three anilide pesticides, namely carboxin, monalide and propanil. DL-PIF-HPLC uses a tunable Nd:YAG-OPO laser to obtain fluorescent photoproduct(s) and to simultaneously analyze their fluorescence in a short acquisition time with an intensified CCD camera, which improves the selectivity (by choosing the suitable excitation wavelength), increases the sensitivity (due to the high energy of the laser beam) and reduces the time of analysis, relative to the classical PIF methods. However, one of the main drawbacks of PIF methods is the presence of interferences with other compounds, such as other pesticides from the same group yielding similar fluorescent photoproducts, which reduces their selectivity. The analytical interest of DL-PIF-HPLC to avoid these interferences is demonstrated. The DL-PIF spectra, chromatographic conditions and analytical performances of DL-PIF-HPLC are presented for the simultaneous determination of three anilide pesticides. The calibration curves are linear over one order of magnitude and the limits of detection are in the ng mL(-1) range. The new DL-PIF-HPLC system has the advantage to combine the performances of both techniques, DL-PIF and liquid chromatography, and to improve the analysis selectivity.
Subject(s)
Carboxin/analysis , Chromatography, High Pressure Liquid/methods , Pesticides/analysis , Propanil/analysis , Spectrometry, Fluorescence/methods , Calibration , Chromatography, High Pressure Liquid/instrumentation , Lasers , Light , Limit of Detection , Methanol , Solutions , Solvents , Spectrometry, Fluorescence/instrumentation , WaterABSTRACT
The electron impact and the hydrogen and methane chemical ionization mass spectra of 5,6-dihydro-2-methyl-1,4-oxathin-3-carboxanilide, the sulfoxide and sulfone derived therefrom, and 2-(2-hydroxyethylthio)-acetoacetanilide enol have been determined. All four compounds show abundant molecular ions in the electron impact spectra and abundant [MH]+ ions in the methane chemical ionization spectra (along with the expected [M + C2H5]+ and [M + C3H5]+ ions), but relatively low [MH]+ ion signals in the hydrogen chemical ionization spectra. From high resolution mass measurements and metastable transitions determined by metastable ion refocusing, electron impact fragmentation mechanisms have been established. For 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide-4-oxide and 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide-4,4-dioxide the major fragmentation mode involves loss of the anilino radical from [M]+, followed by loss of C2H4. Fragmentation to form the aniline molecular ion increases in importance with increasing oxidation state of the sulfur. In the chemical ionization of these three compounds fragmentation of [MH]+ proceeds in a similar fashion by loss of neutral aniline and by formation of protonated aniline. The electron impact mass spectrum of 2-(2-hydroxyethylthio)acetoacetanilide is dominated by the molecular ion and the aniline molecular ion. However, in the chemical ionization mass spectra characteristic fragment ions involving loss of water and loss of aniline from [MH]+, as well as protonated aniline, are observed and serve to characterize the compound.
