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1.
A method for the multiresidue determination of 35 pesticides (30 insecticides and five herbicides) in olive oil by gas chromatography (GC) is described. Three liquid-liquid extraction (LLE) procedures based on (i) partition of pesticides between acetonitrile (ACN) and oil solution in n-hexane, (ii) partition of pesticides between saturated ACN with n-hexane and oil solution in n-hexane saturated with ACN, and (iii) partition of pesticides between ACN and oil were tested for the optimization of the highest pesticide recoveries with the lowest oil residue in the final extracts. Experimental tests were preformed in order to study the efficiency of different clean up procedures with N-Alumina, Florisil, C18, and ENVI-Carb solid-phase extraction (SPE) cartridges for the compounds analyzed by GC-nitrogen phosphorus detection. A second step of clean up was also performed for the compounds analyzed by GC-electron capture detection (ECD), by using phenyl-bonded silica (Ph), diol-bonded silica (Diol), cyanopropyl-bonded silica (CN), and amino propyl-bonded silica (NH2) SPE cartridges. LLE of the oil solution in hexane with ACN followed by an ENVI-Carb SPE clean up of the extract gave the best results for all target compounds. The ACN extract was additionally cleaned through a Diol-SPE cartridge for the determination of pesticides analyzed mainly by GC-ECD. Pesticide recoveries form virgin olive oil spiked with 20, 100, and 500 microg/kg concentrations of pesticides ranged from 70.9 to 107.4%. The proposed method featured good sensitivity, pesticide quantification limits were low enough, and the precision, expressed as relative standard deviation, ranged from 2.4 to 12.0%. The proposed method was applied successfully for the residue determination of the selected pesticides in commercial olive oil samples.  相似文献   

2.
A method was developed to determine organophosphorus pesticides (OPs) in dried ground ginseng root. Pesticides were extracted from the sample using acetonitrile/water saturated with salts, followed by solid-phase dispersive cleanup, and analyzed by capillary gas chromatography with electron ionization mass spectrometry in selective ion monitoring mode (GC-MS/SIM) and flame photometric detection (GC-FPD) in phosphorus mode. The detection limits for most of the pesticides were 0.025-0.05 microg/g using GC-FPD but were analyte-dependent for GC-MS/SIM, ranging from 0.005 to 0.50 microg/g. Quantitation was determined from 0.050 to 5.0 microg/g with r 2 > 0.99 for a majority of the pesticides using both detectors. Recovery studies were performed by fortifying the dried ground ginseng root samples to concentrations of 0.025, 0.1, and 1.0 microg/g, resulting in recoveries of >90% for most pesticides by GC-FPD. Lower (<70%) and higher (>120%) recoveries were most likely from complications of pesticide lability or volatility, matrix interference, or inefficient desorption from the solid-phase sorbents. There was difficulty in analyzing the ginseng samples for the OPs using GC-MS at the lower fortification levels for some of the OPs due to lack of confirmation. GC-FPD and GC-MS/SIM complement each other in detecting the OPs in dried ground ginseng root samples. This procedure was shown to be effective and was applied to the analysis of OPs in ginseng root samples. One particular sample, a ground and dried American ginseng (Panax quinquefolius) root sample, was found to contain diazinon quantified at approximately 25 microg/kg by external calibration using matrix-matched standards or standard addition using both detectors. The advantage of using both detectors is that confirmation can be achieved using GC-MS, whereas the use of a megabore column in GC-FPD can be used to quantitate some of the nonpolar OPs without the use of matrix-matched standards or standard addition.  相似文献   

3.
A new multiresidue method has been developed and validated for the simultaneous determination of 100 pesticide residues in olive oil. The determination of pesticide residues was carried out in only 19 min by gas chromatography coupled to tandem mass spectrometry using a triple quadrupole mass analyzer. The mass spectrometer was operated in electron ionization and the selection reaction monitoring mode was used, acquiring two or three fragmentation reactions per compound. Two extraction processes were studied, and an evaluation of the stability and sensitivity of the chromatographic system has been performed for the tested extraction procedures. The final proposed methodology was based on a liquid-liquid partition with an n-hexane/acetonitrile mixture followed by a gel permeation chromatography cleanup step. An adequate lineal relation was obtained in the studied concentration range (10-200 microg kg (-1)); the recovery values were in the range 70-110% for the two levels of concentration studied: 12 and 50 microg kg (-1). Precision values, expressed as relative standard deviation, were lower than 18% at the aforementioned spiking levels; detection limits, confirmation limits, and quantitation limits were below or equal to 1.9, 2.6, and 3.6 microg kg (-1), respectively. The developed methodology was applied to the analysis of pesticide residues in real samples of olive oil from the south of Spain.  相似文献   

4.
Solid-phase extraction (SPE) and direct competitive chemiluminescence enzyme immunoassay (dcCL-EIA) were combined for the detection of organophosphorus pesticides (OPs) in environmental water samples. dcCL-EIA based on horseradish peroxidase labeled with a broad-specificity monoclonal antibody against OPs was developed, and the effects of several physicochemical parameters on dcCL-EIA performance were studied. SPE was used for the pretreatment of water samples to remove interfering substances and to concentrate the OP analytes. The coupling of SPE and dcCL-EIA can detect seven OPs (parathion, coumaphos, phoxim, quinalphos, triazophos, dichlofenthion, and azinphos-ethyl) with the limit of quantitation below 0.1 ng/mL. The recoveries of OPs from spiked water samples ranged from 62.5% to 131.7% by SPE-dcCL-EIA and 69.5% to 112.3% by SPE-HPLC-MS/MS. The screening of OP residues in real-world environmental water samples by the developed SPE-dcCL-EIA and their confirmatory analysis using SPE-HPLC-MS/MS demonstrated that the assay is ideally suited as a monitoring method for OP residues prior to chromatographic analysis.  相似文献   

5.
An analytical method for the simultaneous determination of 51 pesticides in commercial honeys was developed. Honey (10 g) was dissolved in water/methanol (70:30; 10 mL) and transferred to a C(18) column (1 g) preconditioned with acetonitrile and water. Pesticides were subsequently eluted with a hexane/ethyl acetate mixture (50:50) and determined by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. Pesticides were confirmed by their retention times, their qualifier and target ions, and their qualifier/target abundance ratios. Recovery studies were performed at 0.1, 0.05, and 0.025 microg/g fortification levels for each pesticide, and the recoveries obtained were >86% with relative standard deviations of <10%. Good resolution of the pesticide mixture was achieved in approximately 41 min. The detection limits of the method ranged from 0.1 to 6.1 microg/kg for the different pesticides studied. The developed method is linear over the range assayed, 25-200 microg/L, with determination coefficients of >0.996. The proposed method was applied to the analysis of pesticides in honey samples, and low levels of a few pesticides (dichlofluanid, ethalfluralin, and triallate) were detected in some samples.  相似文献   

6.
A new method to determine pesticide residues in nuts is presented, in which the pesticides are extracted from samples with a small amount of ethyl acetate and anhydrous sodium sulfate. No additional cleanup or concentration steps are necessary. The extract is directly injected into the high-pressure liquid chromatograph, where preseparation of the pesticide residues from other components coextracted from the nuts is carried out using methanol/water as the eluent. The selected liquid chromatography fraction containing the pesticides is automatically transferred to the gas chromatograph using the through-oven transfer adsorption/desorption interface. The calculated limits of detection for each pesticide varied from 0.1 to 61.3 microg/kg. The repeatabilities of the analysis and the overall procedure (extraction and analysis) were satisfactory. No variations in the retention time were observed. The method was applied to the analysis of pistachio nut, peanut, walnut, hazelnut, and sunflower seed.  相似文献   

7.
An analytical multiresidue method for the simultaneous determination of various classes of pesticides in soil was developed. Pesticides were extracted from soil with ethyl acetate. Soil samples were placed in small columns, and the extraction was carried out assisted by sonication. Pesticides were determined by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode. Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. Pesticides were confirmed by their retention times, their qualifier and target ions, and their qualifier/target abundance ratios. Recovery studies were performed at 0.2, 0.1, and 0.05 microg/g fortification levels of each pesticide, and the recoveries obtained ranged from 87.0 to 106.2% with a relative standard deviation between 2.4 and 10.6%. Good resolution of the pesticide mixture was achieved in approximately 41 min. The detection limits of the method ranged from 0.02 to 1.6 microg/kg for the different pesticides studied. The developed method is linear over the range assayed, 25-1000 microg/L, with determination coefficients >0.999. The proposed method was used to determine pesticide levels in real soil samples, taken from different agricultural areas of Spain, where several herbicides and insecticides were found.  相似文献   

8.
A gel permeation chromatographic (GPC) method, used by the U.S. Environmental Protection Agency (USEPA), was modified for cleanup of soil, sediments, wastes, and oily wastes before determination of semivolatile organic pollutants. The modifications included new calibration procedures and control of the amount of material processed. The modifications were evaluated for soil and sediment matrixes in a 5-laboratory study where each laboratory processed a solution containing a phthalate, substituted phenols and benzenes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), nitroaniline, and pesticides. With the exception of nitroaniline, analyte recoveries were 87-112%, with relative standard deviations (RSDs) of 6.7-26%. Soil samples containing PCBs and fortified with 6 pesticides at 0.7-4 micrograms/g were also analyzed by the 5 laboratories. The mean recovery of the 6 pesticides was 100% with a mean RSD of 16%. Mean RSD for the determination of total PCBs was 8.9%. An additional modification for the processing of wastes and high concentration waste samples was attempted; this involved GPC processing of sample extracts dissolved in 1 + 1 butyl chloride-methylene chloride. This modification did not improve recoveries of the semivolatile analytes. Finally, the modified GPC protocol was applied to PCB-contaminated reclaimed waste oils samples. Two GPC cleanup steps were used to separate PCBs from the waste oil samples before PCBs were determined by gas chromatography combined with electron-capture detection (GC/ECD).  相似文献   

9.
A fast, single-step, and efficient partition between n-hexane and acetonitrile on ready-to-use, disposable mini-columns of Kieselghur-type material has been developed for the cleanup of fatty extracts for organophosphate (OP) pesticide residue determination by gas chromatography with flame photometric detection. Nine OP pesticides (diazinon, etrimfos, chlorpyrifos-methyl, pyrimiphos-methyl, chlorpyrifos, bromophos, bromophos-ethyl, malathion, fenitrothion) most commonly used for protection of stored cereals, oil seeds, and legumes were separated from up to 2.0 g lipidic material with recoveries between 80 and 107% at spiking levels ranging for the different compounds from 0.1 to 5.0 ppm.  相似文献   

10.
A method for analysis of 37 pesticide residues in tea samples was developed and validated and was based on reversed-dispersive solid-phase extraction (r-DSPE) cleanup in acetonitrile solution, followed by liquid chromatography-electrospray tandem mass spectrometry determination. Green tea, oolong tea, and puer tea were selected as matrixes and represent the majority of tea types. Acetonitrile was used as the extraction solvent, with sodium chloride and magnesium sulfate enhancing partitioning of analytes into the organic phase. The extract was then cleaned up by r-DSPE using a mixture of multiwalled carbon nanotubes, primary secondary amine, and graphitized carbon black as sorbents to absorb interferences. Further optimization of sample preparation and determination allowed recoveries of between 70% and 111% for all 37 pesticides with relative standard deviations lower than 14% at two concentration levels of 10 and 100 μg kg(-1). Limits of quantification ranged from 5 to 20 μg kg(-1) for all pesticides. The developed method was successfully applied to the determination of pesticide residues in market tea samples.  相似文献   

11.
Five methods using aqueous/organic solvents for the separation of proteins from oils were compared. The extraction with acetone-hexane followed by amino acid analysis was found to be the most suitable method for isolation and quantification of proteins from oils. The detection limit of the method was 0.18 mg protein/kg oil, and the quantification limit was 0.6 mg protein/kg. The relative repeatability limit for samples containing 1-5 mg protein/kg sample was 27%. The protein recovery ranged between 68 and 133%. Using this method, the protein content of 14 refined and nonrefined oils was determined. In none of the refined oils were proteins detected, whereas the protein content of the unrefined oils ranged between undetectable in extra virgin olive oil to 11 mg/kg in rapeseed oil. With sodium dodecyl sulfate-polyacrylamide gel electrophoresis in combination with silver staining, many protein bands were visible in the unrefined soy, olive, peanut, and rapeseed oil samples. Proteins bands were not obtained from the refined fish oil. In the other refined oil samples, a few proteins bands could be visualized. Two protein bands with apparent molecular molecular masses of 58 and 64 kDa were always observed in these oils.  相似文献   

12.
A rapid multiresidue method was developed for the determination of nine organophosphorus pesticides in fruit juices. The analytical procedure is based on the matrix solid-phase dispersion (MSPD) of juice samples on Florisil in small glass columns and subsequent extraction with ethyl acetate assisted by sonication. Residue levels were determined by gas chromatography with nitrogen-phosphorus detection. Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. The NPD response for all pesticides was linear in the concentration range studied with determination coefficients >0.999. Average recoveries obtained for all of the pesticides in the different juices and fortification levels were >70% with relative standard deviations of <11%. The detection limits ranged from 0.1 to 0.6 microg/kg. The identity of the pesticides was confirmed by gas chromatography with mass spectrometric detection using selected ion monitoring. The proposed MSPD method was applied to determine pesticide residue levels in fruit juices sold in Spanish supermarkets. At least one pesticide was found in most of the samples, although the levels detected were very low, far from the maximum residue levels established for raw fruit.  相似文献   

13.
Trace residues of organophosphorus (OP) pesticides are associated with fruits and vegetables that have been sprayed with those OP pesticides to guard against insect pests. Human dietary exposure to these OP pesticides is commonly estimated by measuring the amount of OP metabolites in urine, assuming a stoichiometric relationship between a metabolite and its parent insecticide. Dialkylphosphates (DAPs) are the OP metabolites that are most often used as markers in such biomonitoring studies. However, abiotic hydrolysis, photolysis, and plant metabolism can convert OP chemicals (OP residues) to DAP residues on or in the fruits and vegetables. To evaluate the extent of these conversions, OPs and DAPs were measured in 153 produce samples. These samples from 2 lots were known to contain OP insecticide residues based on routine monitoring by California producers and shippers. A total of 12 OPs were quantified, including mevinphos, naled, acephate, methamidophos, oxidemeton-methyl, azinphos-methyl, dimethoate, malathion, methidathion, phosmet, chlorpyrifos, and diazinon. All OP insecticide residues were below their respective residue tolerances in 2002-2004. A total of 91 of 153 samples (60%) contained more DAP residues than parent OPs. The mean mole fractions [DAPs/(DAPs + OPs)] for the first and second lots of produce were 0.62 and 0.50, respectively, and the corresponding geometric means were 0.55 and 0.34. The corresponding mean mole ratios (DAPs/OP) were 7.1 and 3.4, with geometric means of 2.1 and 0.9. Any preformed DAPs ingested in the diet that are excreted in urine may inflate the estimated absorbed OP insecticide doses in occupational and environmental studies. In subsequent prospective studies, time-dependent production of dimethylphosphate (DMP) and dimethylthiophosphate (DMTP) in strawberries and leaves following malathion sprays occurred concomitant with the disappearance of the parent insecticide and its oxon. DAPs are more persistent in plants and produce at routinely measured levels than their parent OP insecticides.  相似文献   

14.
The application of liquid chromatography time-of-flight mass spectrometry (LC/TOF-MS) for the identification and quantitation of four herbicides (simazine, atrazine, diuron, and terbuthylazine) in olive oil samples is reported here. The method includes a sample treatment step based on a preliminary liquid-liquid extraction followed by matrix solid-phase dispersion (MSPD) using aminopropyl as a sorbent material. A final cleanup step is performed with florisil using acetonitrile as an eluting solvent. The identification by LC/TOF-MS is accomplished with the accurate mass (and the subsequent generated empirical formula) of the protonated molecules [M + H]+, along with the accurate mass of the main fragment ion and the characteristic chlorine isotope cluster present in all of them. Accurate mass measurements are highly useful in this type of complex sample analyses since they allow us to achieve a high degree of specificity, often needed when other interferents are present in the matrix. The mass accuracy typically obtained is routinely better than 2 ppm. The sensitivity, linearity, precision, mass accuracy, and matrix effects are studied as well, illustrating the potential of this technique for routine quantitative analyses of herbicides in olive oil. Limits of detection (LODs) range from 1 to 5 microg/kg, which are far below the required maximum residue level (MRL) of 100 microg/kg for these herbicides in olive oil.  相似文献   

15.
A high-performance liquid chromatography (HPLC) method was developed to quantitatively analyze oleocanthal in extra virgin olive oils. Oleocanthal, a deacetoxy ligstroside aglycone, is known to be responsible for the back of the throat irritation of olive oils and to have probated antiinflamatory activity. Oleocanthal was isolated from small amounts of olive oil sample (1 g) by liquid-liquid extraction. Hexane-acetonitrile was found to be the best solvent system to extract oleocanthal from the oil matrix. The solvent extract was analyzed by reversed-phase HPLC with UV detection at 278 nm. Chromatogaphic separation of oleocanthal from other extracted compounds and of the two geometric isomers of oleocanthal was achieved by an elution gradient with acetonitrile and water. Both the external standard calibration curve and the internal standard calibration curve were established, and quantitation using both calibration curves gave essentially the same result. The reproducibility (RSD = 4.7%), recovery (> 95%), and limit of quantitation (< 1 microg/g) were also determined. Concentrations of oleacanthal in 10 selected throat-burning extra virgin olive oils were determined using the method (ranged from 22 to 190 microg/g) with external standard calibration.  相似文献   

16.
Metal content was determined in 26 samples of virgin argan oil from Morocco. An ETA-AAS with previous sample dilution with MIBK technique was used. In oil obtained by traditional method, Fe ranged from 0.8 to 4.0 mg/kg, Cu from 160.4 to 695.7 microg/kg, Cr from 10.3 to 55.3 microg/kg, Mn from 18.1 to 70.8 microg/kg, and Pb from 28.5 to 450.0 microg/kg. In oil obtained by a half-industrialized method, Fe ranged from 0.8 to 1.7 mg/kg, Cu from 158.4 to 385.0 microg/kg, Cr from 10.0 to 48.1 microg/kg, Mn from 15.0 to 68.5 microg/kg, and Pb from 32.0 to 100.0 microg/kg. Acidity value, peroxide index, K270 and K232, humidity and sludge volatile, and insoluble sludges in petroleum ether were also determined. A high variability in these quality parameters and a decrease of the quality in the oils obtained by the traditional method were observed.  相似文献   

17.
alpha-Tocopherol, the main tocopherol homologue found in olive oil, was determined using normal phase HPLC. Ninety Greek virgin olive oils, selected according to a designed sampling protocol from different cultivars and regions all over Greece for three successive crop years, were analyzed. For a specific olive cultivar, which is widely used for the production of olive oil in Greece, additional measurements were made to study the effect of milling conditions on alpha-tocopherol concentration. Finally, a significant number of commercial olive oil samples (25) obtained from the retail market were analyzed. High concentrations of alpha-tocopherol were observed in most of the samples selected from various regions. Values ranging between 98 and 370 mg/kg were found (>200 mg/kg in 60% of samples). Extraction conditions were not found to influence alpha-tocopherol level. alpha-Tocopherol content of retail market samples was high, ranging from 120 to 250 mg/kg of oil (>180 mg/kg in 60% of samples). Storage of samples under domestic conditions for two years showed that good handling is quite important for retaining high alpha-tocopherol levels and for increasing, thus, the storage life and nutritional value of this exquisite oil.  相似文献   

18.
High-field 31P NMR (202.2 MHz) spectroscopy was applied to the analysis of 59 samples from three grades of olive oils, 34 extra virgin olive oils from various regions of Greece, and from different olive varieties, namely, 13 samples of refined olive oils and 12 samples of lampante olive oils. Classification of the three grades of olive oils was achieved by two multivariate statistical methods applied to five variables, the latter being determined upon analysis of the respective 31P NMR spectra and selected on the basis of one-way ANOVA. The hierarchical clustering statistical procedure was able to classify in a satisfactory manner the three olive oil groups. Subsequent application of discriminant analysis to the five selected variables of oils allowed the grouping of 59 samples according to their quality with no error. Different artificial mixtures of extra virgin olive oil-refined olive oil and extra virgin olive oil-lampante olive oil were prepared and analyzed by 31P NMR spectroscopy. Subsequent discriminant analysis of the data allowed detection of extra virgin olive oil adulteration as low as 5% w/w for refined and lampante olive oils. Further application of the classification/prediction model allowed the estimation of the percent concentration of refined olive oil in six commercial blended olive oils composed of refined and virgin olive oils purchased from supermarkets.  相似文献   

19.
Twenty-three laboratories from 13 countries in continental Europe, Scandinavia, the British Isles, and North America participated in a polychlorinated biphenyl (PCB) Check Sample Program conducted under the auspices of the International Council for Exploration of the Sea (ICES). PCBs were determined in unspiked and spiked (1.00 mg Aroclor 1254/kg oil) herring (Clupea harengus harengus) oil by the participants, each of which used his or her own cleanup and quantitation techniques; a common Aroclor 1254 mixture was used as a standard and a common quantitation technique was used for comparative purposes. Results for the unspiked oil ranged from 0.48 to 3.416 mg PCB/kg oil, while spiked oil results ranged from 0.70 to 3.891 mg/kg. Calculated spike recoveries ranged from 22 to 136%. Serious deficiencies were found in most steps in the procedures. No evidence was found to support the use of a common PCB standard or a common method of calculation using packed column chromatography. The chromatographic stationary phase used appeared to affect the PCB levels obtained. Florisil cleanup adsorbent yielded higher mean results for both unspiked and spiked oils than did alumina. Large coefficients of variation were found (25-50%), the principal source of which was systematic error (interlaboratory).  相似文献   

20.
A gas chromatographic method for the analysis of 10 organochlorine pesticides in 0.5 mL of whole blood is described. Sample preparation involved an ethyl ether and hexane extraction, followed by a silica solid phase extraction cleanup. The pesticides are quantified by gas chromatography/electron capture detection. Method limits of detection ranged from 1.1 to 5.2 microg/L. The mean and standard deviation for the recovery of 10 pesticides was 97.9 +/- 5.5%. Recoveries from whole blood were comparable to recoveries from plasma. This indicates that the preparation of plasma is unnecessary for the quantification of organochlorine pesticides in blood. This approach is particularly useful as a nonlethal approach for monitoring pesticide contamination in small animals for which the volume of blood is limiting.  相似文献   

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