Determination of nine organophosphorus pesticides in cereals and kidney beans by capillary gas chromatography with flame photometric detection

A method is developed for the determination of nine organophosphorus pesticide residues in cereals and kidney beans by capillary gas chromatography with flame-photometric detection. In this method, dichloromethane is used for clean-up after liquid-liquid extraction. It is shown that good separations are obtained using a fused-silica capillary column (DB-1701) by the optimized temperature program. In the spiked levels of 0.012-0.43 mg/kg, the recoveries are from 83.7% to 107%, with the relative standard deviation between 3.2% and 13% and limits of detection from 8.2 to 15 microg/kg. The method is rapid, sensitive, and practical.     

Potential of microcolumn liquid chromatography and capillary electrophoresis with flame photometric detection for determination of polar phosphorus-containing pesticides

Summary The potential of microcolumn liquid chromatography (μlC) and capillary electrophoresis (CE) with on-line, flame photometric detection (FPD) in the P-selective mode has been studied for determination of polar P-containing pesticides, glyphosate and its main metabolite, aminomethylphosphonic acid (AMPA), ethephon, fosetyl-aluminium and acephate. Acephate was determined by reversed-phase μLLC-FPD using large-volume injections with peak compression, the other compounds were determined by μLC-FPD and CE-FPD using simple, large-volume injection procedures to obtain limits of detection of 7.5-500 ng·mL⁻¹ and 1.0 μ·mL⁻¹, respectively. The methods showed acceptable repeatability and robustness and were successfully applied for rapid and selective determination of pesticides in fruit, vegetable and water samples.     

Determination of organophosphorus pesticides in Lycium barbarum by gas chromatography with flame photometric detection

An analytical method was developed to determine 14 organophosphorus pesticide residues in Lycium barbarum, which is both a botanical medicine and a food. A 5 g sample is mixed with 10 mL ethyl acetate and, after shaking and centrifuging, 5 mL of the upper layer is removed, concentrated, and analyzed by gas chromatography (GC) with flame photometric detection. The essential feature of this method is that, for the purpose of reducing the burden of the GC system, 0.01 g activated carbon is used to absorb pigments during the cleanup procedure. Average recoveries of 14 organophosphorus pesticides added at 0.05, 0.1, and 0.5 mg/kg were 66.84-102.42, 71.07-97.93, and 62.50-96.24%, respectively. Limits of detection ranged from 5 to 15 microg/kg. The identities of the 14 pesticides were confirmed by GC/mass spectrometry detection in the selected-ion monitoring mode. This method is sensitive, simple, rapid, inexpensive, and safe.     

Automated determination of nifedipine in human plasma by capillary gas chromatography with electron capture detection

A rapid, sensitive, and reliable method for the determination of nifedipine in human plasma is described. Using a single-step solvent extraction and capillary gas chromatography combined with electron capture detection, an assay sensitivity of 2 ng/ml is achieved routinely using 0.5 ml of plasma. Intact nifedipine is quantitated and separated from its nitroso- and nitropyridine-derivatives. The suitability of the assay for pharmacokinetic studies is illustrated.     

Development of a method for the determination of 9 currently used cotton pesticides by gas chromatography with electron capture detection

A reliable, sensitive, and reproducible method was developed for quantitative determination of nine new generation pesticides currently used in cotton agriculture. Injector temperature significantly affected analyte response as indicated by electron capture detector (ECD) chromatograms. A majority of the analytes had an enhanced response at injector temperatures between 240 and 260 degrees C, especially analytes such as acephate that overall had a poor response on the ECD. The method detection limits (MDLs) were 0.13, 0.05, 0.29, 0.35, 0.08, 0.10, 0.32, 0.05, and 0.59 ng/mL for acephate, trifuralin, malathion, thiamethozam, pendimethalin, DEF6, acetamiprid, brifenthrin, and lambda-cyhalothrin. This study provides a precision (0.17-13.1%), accuracy (recoveries=88-107%) and good reproducible method for the analytes of interest. At relatively high concentrations, only lambda-cyhalothrin was unstable at room temperature (20-25 degrees C) and 4 degrees C over 10 days. At relatively low concentrations, acephate and acetamiprid were also unstable regardless of temperature. After 10 days storage at room temperature, 30-40% degradation of lambda-cyhalothrin was observed. It is recommended that acephate, acetamiprid, and lambda-cyhalothrin be stored at -20 degrees C or analyzed immediately after extraction.     

Residue analysis of organophosphorus pesticides in food with two-dimensional gas chromatography using capillary columns and flame photometric detection

Two-dimensional gas chromatography with two capillary columns of different polarity (SP 2100 and OV 225) is used for pesticide residue analysis in food samples. By means of “live chromatography” applying pneumatic switching technique according to Deans, unequivocal identification of 57 organophosphorus pesticides in food samples is achieved at trace concentrations. The instrument is equipped with only one injection port and one flame photometric detector. On-line data processing is very helpful, especially in calibration and checking the system's reliability with the multitude of test compounds. The complete pesticide residue analysis including clean-up of about six food samples can be completed by one person in 8 hours.     

Multiresidue determination of organophosphorus pesticides in ginkgo leaves by accelerated solvent extraction and gas chromatography with flame photometric detection

A rapid and simple method using accelerated solvent extraction and solid-phase extraction cleanup was developed and validated for the determination of 15 organophosphorus pesticides in ginkgo leaves by capillary gas chromatography with flame photometric detection. The pesticides were extracted at 100 degrees C under 1500 psi pressure in <20 min. The average recovery from 10 g ginkgo leaves, fortified at 3 levels ranging from 0.05 to 1.00 mg/kg, was 95.2% with a relative standard deviation of 4.6%. The limits of detection ranged from 1.11 x 10(-3) mg/kg (dimethoate) to 4.44 x 10(-3) mg/kg (dichlorvos). The proposed method showed acceptable accuracy and precision while minimizing environmental concerns, time, and labor. Furthermore, the method could be easily applied to the monitoring of these 15 organophosphorus pesticides in ginkgo leaves.     

On-line determination of organochlorine pesticides in water by solid-phase microextraction and gas chromatography with electron capture detection

This paper describes the extraction of 20 organochlorine pesticides (OCPs) from water samples using solid-phase microextraction (SPME). Three fused-silica fibers coated or bonded with polydimethylsiloxane (PDMS) of different film thicknesses (20-, 30-, and 100-μm) were evaluated. The extraction time, the effects of stirring and addition of NaCl to the aqueous sample, the linear range and the precision of this technique, and the effect of carryover were examined for 20 analytes and are presented here. A comparison with results using conventional liquid-liquid extraction demonstrate that the SPME technique is well suited as a fast screening technique for OCPs in water samples.     

Determination of coumarin in fragrance products by capillary gas chromatography with electron capture detection.

A gas chromatographic (GC) method is described for the determination of coumarin in fragrance products. Coumarin was tentatively identified by retention time and confirmed by GC/mass spectrometry. The amount of coumarin was determined by external standard. The method was validated by conducting recovery studies from fortified fragrance products at several concentrations. Recoveries of coumarin ranged from 99 to 110%, with a relative standard deviation of 3.24. The method was used to survey a variety of fragrance products purchased in the metropolitan Washington, DC area, for coumarin. Seventy one percent of the products were found to contain coumarin at concentrations ranging from 0.002 to 0.61%.     

Direct Grignard pentylation of organotin-contaminated lard samples followed by capillary gas chromatography with flame photometric detection

During a recent investigation of the organotin-contaminated lard samples, a simple method was developed by direct Grignard pentylation of lard samples and capillary gas chromatography with flame photometric detection using quartz surface-induced tin emission. Using HP-1 capillary column with temperature programming and FPD detector, pentylated tri-, di-, monometyltin, dioctyltin and Sn(IV) can be base-line separated and detected within 20 min. The analysis of pentylated tin compounds by GC-MS confirmed the existence of methyltins and inorganic tin in lard samples, which was agreeable with the results obtained by GC-FPD. The content of organotin compounds was calculated by internal standard method in which methyltripropyltin (MeSnPr3) acted as internal standard. The results showed that these samples were heavily contaminated with mg/g levels of dimethyltin, microg/g levels of tri- and monomethyltin. Among them, one sample contained mg/g level of dioctyltin and one contained a little of inorganic form of Sn(IV). The recoveries of tri-, di- and monomethyltin were 95.7%, 105.5% and 105.7%, respectively.     

Broad-spectrum determination of pesticides in groundwater by gas chromatography with electron capture detection, nitrogen-phosphorus detection, and tandem mass spectrometry.

Gas chromatography with electron capture detector (ECD), nitrogen-phosphorus detector (NPD), and tandem mass spectrometry (MS/MS) was used to identify 36 pesticides, widely used to control various pest and diseases in vegetables, in water after a preconcentration step on C18 cartridges. The recoveries obtained ranged from 70 to 135% at a fortification level of 100 ng/L with relative standard deviations of <36.2%. The limits of detection and quantitation were < or =48 and < or =160 ng/L, respectively. Important advantages of MS/MS over ECD and NPD in the determination of pesticides are also presented. The proposed analytical methodology was applied to the determination of pesticides in groundwater samples from an agricultural area, the Campo de Dalías (Almería, Spain). The most frequently encountered pesticides were endosulfan sulfate and metalaxyl, whereas the pesticide found at the highest concentration was fenamiphos.     

Analysis of polynuclear aromatic hydrocarbons by glass capillary gas chromatography using simultaneous flame ionization and electron capture detection

The possibility of simultaneous application of an electron capture (ECD) and a flame ionization detector (FID) connected to a glass capillary column for analyzing polynuclear aromatic hydrocarbons (PNA) has been investigated. The ECD/FID ratio is determined for 46 PNA compounds. The ratios vary from 0.02 to 117 with relative standard deviations better than 20 percent determined from 10 replicate analyses. The results suggest that the method may be used for obtaining additional evidence in identifying PNA in environmental samples. Impurities and transformation products in the standard were identified by computerized glass capillary gas chromatography/mass spectrometry. Quinones and diones are responsible for the high EC-response determined in some trace components in the standard. An application of the method is shown for PNA from particulates in urban atmospheres.     

Determination of methylmercury in biological samples by capillary gas chromatography with electron capture detection

A precise and accurate method has been developed for the determination of methylmercury in biological material using capillary gas chromatography with electron-capture detection. Homogenized fish or mussel samples were digested with acid, spiked with ethylmercury chloride as an internal standard and extracted with toluene. After treatment of the solvent extract with sodium thiosulphate and cupric bromide the alkylmercurials were extracted into benzene as their bromide derivatives and analyzed using an OV-275 coated glass capillary column. The detection limit of the method for methylmercury was 5 g/kg tissue.     

Application of solvent sublation for the determination of organophosphorous pesticides in vegetables by gas chromatography with a flame photometric detector.

An effective method for separating and enriching organophosphorous pesticides (OPPs) from vegetables by solvent sublation and the OPPs determination by gas chromatography with flame photometric detector (GC-FPD) has been developed. The effects of organic solvent, nitrogen flow rate, pH of the solution, sublation time etc. on the sublation efficiency of OPPs were investigated in detail, and the optimal conditions of solvent sublation were selected. The floated product of vegetables in the optimal conditions was determined by GC-FPD. The limits of detection (LODs) ranged from 1.2 microg kg-1 (for dimethoate) to 3.5 microg kg-1 (for chlorpyrifos). The recoveries of spiked vegetable samples were from 81.3 to 98.9%, and RSD values were from 0.46 to 4.83%. The results show that this method is simple, sensitive and rapid.     

Interference from elemental sulphur in the determination of organotins by gas chromatography with flame photometric detection

Elemental sulphur, a common constituent of marine sediments, has been shown to give dialkyl sulphides with the Grignard reagents commonly used to derivatize alkyltin species before their determination by gas chromatography with flame photometric detection (GC–FPD). Further, it has been demonstrated that even with the red filter for 610 nm (normally used for organotin compounds) fitted to the detector, sulphur compounds do give rise to an emission signal, which may be mistaken for tin emission from a pentylated or propylated alkyltin compound, as the respective retention times are in some cases quite close. © 1997 by John Wiley & Sons, Ltd.