A multi-residue method for pesticide residue analysis in rice grains using matrix solid-phase dispersion extraction and high-performance liquid chromatography–diode array detection

Pesticides are widely used in rice cultivation, often resulting in detection of their residues in rice grains. So far, no analytical method has been available for the simultaneous determination of most rice pesticides in rice grains. This paper reports the development and validation of such a method for the determination of eight rice pesticides (penoxsulam tricyclazole, propanil, azoxystrobin, molinate, profoxydim, cyhalofop-butyl, deltamethrin) and 3,4-dichloroaniline, the main metabolite of propanil. Pesticide extraction and clean-up was performed by an optimized matrix solid-phase dispersion (MSPD) protocol on neutral alumina (5 g) using acetonitrile as the elution solvent. Samples were analyzed in a high-performance liquid chromatography–diode array detection (HPLC-DAD) system. Pesticide separation was achieved with a mobile phase of acetonitrile/water in a linear elution gradient from 30:70% (v/v) to 100:0% (v/v) in 14 min at a flow rate of 0.8 mL min^?1. Method validation was performed by means of linearity, intra-day accuracy, inter-day precision and sensitivity. Linear regression coefficients (R ²) were always above 0.9948. Limits of detection (LOD) and quantification (LOQ) varied from 0.002 to 0.200 mg kg^?1 and 0.006 to 0.600 mg kg^?1, respectively. Recoveries were investigated at three fortification levels and were found to be acceptable (74–127%) with relative standard deviations (RSD) below 12%. Application of the method for the analysis of five commercial rice grain samples showed that the pesticide levels were below the LOD. Overall, the method developed is suitable for the determination of residues of most rice pesticides in rice grains at levels below the established MRLs.     

Determination of malathion, coumaphos, and fluvalinate residues in honey by gas chromatography with nitrogen-phosphorus or electron capture detectors

A rapid, reliable, and inexpensive extraction method was developed to determine acaricide residues in honey by gas chromatography (GC) with nitrogen-phosphorus (NP) or electron capture (EC) detectors. Because of the high selectivity of the NP detector, no interfering peaks were present and no cleanup was necessary. A simple cleanup step is proposed for the GC-ECD analysis. Recoveries from spiked honey samples ranged from 79 to 94.4%, with coefficients of variation of 0.3-18.5%. The quantitation limit obtained was 0.015 mg/kg for malathion, 0.020 mg/kg for coumaphos, and 0.005 mg/kg for fluvalinate. The method was used to determine the disappearance of malathion and coumaphos residues from honey samples collected from beehives treated with these acaricides. The disappearance of both acaricides was rapid and followed a first-order model for the duration of the experiment.     

Development and validation of an HPLC-DAD method for the simultaneous determination of most common rice pesticides in paddy water systems

Rice crop is mainly cultivated in large river basins which constitute unique ecosystems and their ecological quality is invaluable. However, the high loads of pesticides used in rice cultivation contribute to the contamination of the water resources in such rice-cultivated regions. To regularly monitor the quality of such water resources there is a need for a rapid and sensitive multi-residue analytical method. This study presents the development and validation of a new analytical method for the simultaneous determination of most rice pesticides including penoxsulam, tricyclazole, propanil and its main metabolite 3,4-dichloroaniline, azoxystrobin, molinate, profoxydim and deltamethrin. A solid-phase extraction (SPE) procedure followed by high performance liquid chromatography (HPLC) with diode array detection (DAD) was used. A C₁₈ RP column operated at 30°C was utilised and the analytes were separated with a mobile phase of acetonitrile/water mixture in a linear gradient. Clean-up of water samples and isolation of pesticides was performed on SPE Bakerbond octadecyl cartridges and an ethyl acetate-dichlomethane mixture (9?:?1 v/v, 2?mL) was used for elution. Method validation was performed by means of intra-day (n?=?5) and inter-day accuracy and precision (n?=?8), sensitivity and linearity. The relative recoveries of the pesticides in paddy water samples were acceptable (80.6–110.2%) and the relative standard deviation (RSD%) ranged from 1.9 to 7.6%. Limits of detection (LOD) and limits of quantification (LOQ) varied from 0.1 to 0.8?ng?mL^?1 and 0.25 to 2.0?ng?mL^?1 respectively, depending on the analyte. The method was subsequently applied for the determination of pesticide residues in paddy and canal water samples. Tricyclazole was the most frequently detected pesticide at the highest concentrations, while herbicides were less frequently detected and at lower concentrations. The method described could be a valuable tool for regular monitoring of surface water systems in rice-cultivated basins.     

New multiresidue method using solid-phase extraction and gas chromatography-micro-electron-capture detection for pesticide residues analysis in royal jelly

Royal jelly, one of the most important bee products, can be contaminated with pesticide and/or antibiotic residues resulting from treatments applied either inside beehives or in the agricultural environment. A new multiresidue method was developed and validated for analysis of nine pesticides in royal jelly. Solid-phase extraction RP-C(18) cartridges were used for sample purification and isolation of analytes. Final solution was analyzed with GC and micro-electron-capture detection. Four synthetic acaricides used by beekeepers (bromopropylate, coumaphos, malathion and tau-fluvalinate), and moreover one pyrethroid, two organochlorine, and two organophosphate insecticides were tested. Linearity is demonstrated for the range of 0.0025-1mgkg(-1), with correlation coefficients ranging from 0.99991 to 0.99846, depending on the analyte. Overall recovery rates from royal jelly blank samples spiked at five fortification levels ranged from 80.8% (lindane) to 91.3% (ethion), well above the range defined by the SANCO/10232/2006 and EC/675/2002 documents. The limit of quantification was <0.003-0.005 mg kg(-1) depending on the analyte, and the reporting level of the method, defined as the lowest recovery level, was 0.005 mg kg(-1).     

Determination of fluvalinate residues in beeswax by gas chromatography with electron-capture detection

A simple, rapid, and accurate method is described for the determination of residual fluvalinate in beeswax. The procedure consists of partitioning on a disposable column of diatomaceous earth (Extrelut), followed by chromatographic cleanup on a Florisil cartridge. The final extract is analyzed by capillary gas chromatography with electron-capture detection (GC-ECD). Briefly, wax samples were dissolved in n-hexane, and the solutions were sonicated and transferred to Extrelut columns. The fluvalinate was extracted with acetonitrile, and a portion of the extract was cleaned up on a Florisil cartridge. The fluvalinate was eluted with diethyl ether-n-hexane (1 + 1) and directly determined by GC-ECD. Recoveries from wax samples spiked at 5 fortification levels (100-1500 microg/kg) ranged from 77.4 to 87.3%, with coefficients of variation of 5.12-8.31%. The overall recovery of the method was 81.4 +/- 3.2%, and the limit of determination was 100 microg/kg.