Multiresidue Determination of Pesticide Residues in Honey by Modified QuEChERS Method and Gas Chromatography with Electron Capture Detection (original) (raw)
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[Determination of multiple pesticide residues in honey using gas chromatography-mass spectrometry]
Se pu = Chinese journal of chromatography / Zhongguo hua xue hui, 2006
An analytical method was developed for the simultaneous determination of 23 pesticide residues in various commercial honeys. Meanwhile, the characteristic ions and fragmentation mechanism of three pesticides in the process of electron ionization mass spectrometry (EI/MS) were evaluated. After the optimization of different parameters such as the extraction solvent, pesticides were extracted from honey with ethyl acetate in an ultrasonic bath, cleaned up on a Florisil column by an elution of mixture of hexane and ethyl acetate (7:3, v/v), and analyzed by gas chromatography-electron ionization mass spectrometry (GC-EI/MS) in the selected ion monitoring mode (SIM) with PCB103 as internal standard. Recovery studies were performed at 50, 100 and 200 microg/kg fortification levels for each pesticide, and the recoveries ranged from 82% to 120% with relative st0ndard deviations between 1.8% and 11.0% for different pesticides. The limit of detection was less than 10.0 microg/kg for all the pe...
2012
Honey is an important food widely used by people around the world. It can contain agrochemical residues as a result of the use of these products in agriculture. QuEChERS method was used for the determination of seven pesticide residues (chlorothalonil, heptachlor, captan, α-endosulfan, β-endosulfan, endosulfan sulfate and dieldrin) in 25 Brazilian honey samples from different regions. Extraction was carried out through the use of 1% acetic acid-ethyl acetate solvent with MgSO 4 and CH 3 COONa, followed by dSPE cleanup with PSA sorbent. The analyses were carried out with GC-µECD. The chromatographic signal showed good linearity with correlation coefficient ≥ 0.99 and the LOQs for the pesticides studied varied between 0.007 to 0.05 mg kg -1 . The method was validated using a blank sample of honey spiked at three fortification levels (0.07, 0.2 and 0.4 mg kg -1 ). The recoveries for the seven compounds ranged from 75% to 119%, and relative standard deviations were ≤ 26%. Five of the 25 honey samples analyzed contained pesticide residues, with a maximum concentration of 0.026 mg kg -1 for α-endosulfan. From the five contaminated samples, four were from non-agricultural areas, which indicated environmental contamination at these sites. The QuEChERS approach was successfully employed for the GC-µECD analyses of the seven studied pesticides in honey samples.
Chromatographic-based methods for pesticide determination in honey: An overview
Talanta, 2007
Nowadays the control of pesticides in honey is an issue of primary health importance as consequence of the increasing content of these chemicals in the aforementioned matrix. This poisoning has led to the worldwide increasing loss of bees since 1995. From Europe to Canada, scientist, beekeepers and chemical companies disagree about the reasons that have led to colony losses higher than 50% in some areas. This problem has become a public health issue due to the high honey worldwide consumption. The presence of pesticides in honey has been directly related to bees' mortality by some researchers through pesticide presence in (1) pollen, (2) honeycomb walls, (3) own bees and (4) honey. In this work we describe the actual state-of-the-art for pesticides determination in honey along with a review in this subject focused on sample treatments and instrumentation. Finally, future trends are also commented.
Determination of Selected Pesticides in Honey by LC-MS-It: Effects of Sample Preparation
Safety Engineering, 2012
Honey is well known in human diet and it is considered to be one of the healthiest foods with high nutritional value. Due to the growing presence of anthropogenic contaminants, with extremely long half-life and prevalence in all environments, some of them may be present in honey. Honey samples were spiked with six pesticides which are commonly used at the time of plant's blooming, in order to develop an efficient method for preparing honey samples for LC-MS-IT analysis. Samples of honey, spiked with soultion containing mixture of six pesticides (pirimicarb, atrazine, prometrine, malation, cyprodinil and famoxadone), were treated applying SPE with Florisil and C18 cartriges, as well as liquid-liquid extraction method. Afterwards, samples were injected in the HPLC with ESI ionisation source, and IT (ion trap) mass analyzer. Methanol solution of pesticides in the same concentrations as in spiked samples, were used as blank. In spiked honey samples, after treatment with Florisil pro...
Journal of chromatography. A, 2007
We report on the development and validation under ISO 17025 criteria of a multi-residue confirmatory method to identify and quantify 17 widely chemically different pesticides (insecticides: Carbofuran, Methiocarb, Pirimicarb, Dimethoate, Fipronil, Imidacloprid; herbicides: Amidosulfuron, Rimsulfuron, Atrazine, Simazine, Chloroturon, Linuron, Isoxaflutole, Metosulam; fungicides: Diethofencarb) and 2 metabolites (Methiocarb sulfoxide and 2-Hydroxytertbutylazine) in honey. This method is based on an on-column liquid–liquid extraction (OCLLE) using diatomaceous earth as inert solid support and liquid chromatography (LC) coupled to mass spectrometry (MS) operating in tandem mode (MS/MS). Method specificity is ensured by checking retention time and theoretical ratio between two transitions from a single precursor ion. Linearity is demonstrated all along the range of concentration that was investigated, from 0.1 to 20 ng g−1 raw honey, with correlation coefficients ranging from 0.921 to 0.999, depending on chemicals. Recovery rates obtained on home-made quality control samples are between 71 and 90%, well above the range defined by the EC/657/2002 document, but in the range we had fixed to ensure proper quantification, as levels found in real samples could not be corrected for recovery rates. Reproducibility is found to be between 8 and 27%. Calculated CCα and CCβ (0.0002–0.943 ng g−1 for CCα, and 0.0002–1.232 ng g−1 for CCβ) show the good sensitivity attained by this multi-residue analytical method. The robustness of the method has been tested in analyzing more than 100 raw honey samples collected from different areas in Belgium, as well as some wax and bee samples, with a slightly adapted procedure.
Foods
This study aimed to optimize and validate a multi-residue method for identifying and quantifying pesticides in honey by using both gas and liquid chromatographic separation followed by mass spectrometric detection. The proposed method was validated to detect 168 compounds, 127 of them by LC-MS/MS (liquid chromatography tandem mass spectrometric detection) and 41 by GC-MS/MS (gas chromatography tandem mass spectrometric detection). The limit of detection (LOD) and limit of quantification (LOQ) values for the analytes determined by LC-MS/MS were 0.0001–0.0004 mg/kg and 0.0002–0.0008 mg/kg, respectively. For GC-MS/MS analyses, the LOD and LOQ values were 0.001–0.004 mg/kg and 0.002–0.008 mg/kg. In total, 33 samples of commercial honey produced by apiaries in six Brazilian states were analyzed with the validated method. Residual amounts of 15 analytes were detected in 31 samples (93.9%). The method described in the present study was able to detect an extensive and broad range of pestici...
Screening of multiclass pesticide residues in honey by SPE-GC/MSD: a pilot study
Environmental Monitoring and Assessment, 2018
In the present study, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was proposed for the simultaneous analysis of 75 pesticides in maca and Moringa oleifera with ultraperformance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/ MS). The developed method was validated in accordance with linearity, linear range, limit of detection, limit of quantification, accuracy, precision, and matrix effect. Each analyte had good linearity (R 2 > 0.99) in the corresponding concentration range. The method LOD and LOQ values of all the analytes ranged from 0.01 mg kg À1 to 303.35 mg kg À1 and 0.03 mg kg À1 to 1011.15 mg kg À1 , respectively. The recoveries (n ¼ 6) of the analyzed pesticides were in the range of 75.92-113.43%. The RSDs of precision were between 0.60% and 7.36%. All matrix effect values ranged from 81.79% to 118.71% and 80.36% to 119.64% in maca and Moringa oleifera, respectively. The analysis of 103 samples showed the presence of isofenphos-methyl in some of them. The method had a good application prospect and could be used as a general approach for the quantitative determination of pesticide residues in food.
Journal of Chromatography A, 2011
The feasibility of different extraction procedures was tested and compared for the determination of 12 organophosphorus and carbamates insecticides in honey samples. In this sense, once the samples were pre-treated-essentially dissolved in hot water by stirring-and before they could be analyzed by liquid chromatography-ion trap-second stage mass spectrometry (LC-MS 2), four different approaches were studied for the extraction step: QuEChERS, solid-phase extraction (SPE), pressurized liquid extraction (PLE) and solid-phase microextraction (SPME). The main aim of this work was to maximise the sensitivity of pesticides and to minimise the presence of interfering compounds in the extract. All pesticides were linear in the range from CCˇto 1000× CCˇfor the four extraction methods (three orders of magnitude). Detection capabilities (CCˇ) were 0.024-1.155 mg kg −1 with QuEChERS, 0.010-0.646 mg kg −1 with SPE, 0.007-0.595 mg kg −1 with PLE, and 0.001-0.060 mg kg −1 with SPME. All the target compounds could be recovered by any of the methods, at a CCˇfortification level ranged from 28 to 90% for the SPME. In comparison, the PLE method was the most efficient extraction method with recoveries from 82 to 104%. It was followed by the QuEChERS method with recoveries between 78 and 101% and the SPE method with recoveries between 72 and 100%. The repeatability expressed as relative standard deviation (RSDs) was below 20% for all the pesticides by any of the tested extraction methods. Results obtained applying the four extraction techniques to real honey samples are analogous.
Determination of pesticide residues in sugarcane honey by QuEChERS, and liquid chromatography
Journal of the Brazilian Chemical Society, 2012
Neste trabalho, é descrito um método para determinação dos agrotóxicos 2,4-D, diurom e fipronil em mel de cana-de-açúcar. O método QuEChERS foi empregado para extração e a quantificação foi realizada por cromatografia líquida de alta eficiência acoplada ao detector por arranjo de diodos (HPLC-DAD) e cromatografia líquida acoplada à espectrometria de massas sequencial com fonte de ionização por eletronebulização (LC-ESI-MS/MS). Após a otimização dos parâmetros de extração e determinação dos agrotóxicos, o método foi validado avaliando-se a curva analítica, linearidade, limites de detecção e quantificação, precisão (repetibilidade) e exatidão (recuperação). Devido à ocorrência do efeito de matriz, a quantificação foi realizada com os padrões analíticos preparados no extrato branco da matriz. O método apresentou limites de detecção na faixa de 0,016-0,1 mg kg -1 por HPLC-DAD e de 0,00016-0,0008 mg kg -1 por LC-ESI-MS/MS. O método foi empregado na determinação de agrotóxicos em mel de cana-de-açúcar.
Food Chemistry, 2007
A simple and fast multiresidue method has been developed to determine 48 pesticides within the major groups of pesticides (organohalogen, organophosphorous, pyrethroids and organonitrogen) in representative samples of locally produced honey, in Bauru (State of São Paulo, Brazil) during 2003-2004. The recovery results found ranged from 76% to 95% and the limits of detection were lower than 0.01 mg/kg for gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). The results indicated that most pesticides found in the samples belonged to the organohalogen and organophosphorous groups and lower levels of residues of some organonitrogen and pyretroids were also detected. Malathion residues were detected in all the samples, in a high concentration, owing to its applications to control dengue mosquitoes in the area studied.