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1.
An analytical method for the simultaneous determination of residues of eight neonicotinoid insecticides and two metabolites in honey using LC-MS/MS was developed and validated. Two approaches of sample preparation were investigated, with the final method involving acetonitrile extraction and subsequent cleanup by dispersive solid-phase extraction (QuEChERS type). Validation was based on quintuplicate analysis at three fortification levels and showed satisfactory recoveries (60-114%) and high precision (RSDs between 2.7 and 12.8%). Low limits of detection and quantification could be achieved for all analytes ranging from 0.6 to 5 μg/kg and from 2 to 10 μg/kg, respectively. Investigations of Austrian honey samples revealed the presence of acetamiprid, thiacloprid, and thiamethoxam residues in honey; however, no sample exceeded the maximum residue limits. On average, flower honey samples contained neonicotinoid residues in higher quantities compared to forest honey samples.  相似文献   

2.
Ractopamine hydrochloride is a beta-adrenergic leanness-enhancing agent approved for use in swine in the United States. Depletion of ractopamine and its metabolites from animal tissues, urine, and serum is of interest for the detection of illegal use. The objectives of this study were to measure the residues of ractopamine in swine incurred samples after treatment with dietary ractopamine for 28 consecutive days. An efficient and sensitive analytical method was developed for the detection of parent ractopamine and its metabolites in swine tissues, urine, and serum by HPLC-FLD. After extraction, enzymatic digestion, and solid-phase cleanup of the samples, ractopamine residues were determined by liquid chromatography (LC) with fluorescence detector. The limits of detection (LOD) for tissues, urine, and serum were 1 ng g(-1), 0.5 ng mL(-1), and 0.5 ng mL(-1), respectively. Recoveries ranged from 70.5 to 94.5% for samples fortified at 1-50 ng g(-1) or ng mL(-1). Sixty pigs were fed twice daily for 28 consecutive days with feeds containing 18 mg kg(-1) ractopamine HCl. The residue concentrations in urine, liver, and kidney were 650.06 ng mL(-1), 46.09 ng g(-1), and 169.27 ng g(-1), respectively, compared with those in muscle, fat, and serum (4.94 ng g(-1), 3.28 ng g(-1), and 7.48 ng mL(-1), respectively) at the feeding period of 7 days. The residue concentrations at withdrawal period of 0 days in all edible tissues were lower than tolerance values established by the FDA and MRL values listed by the JECFA. These data support the withdrawal time of 0 days established by the FDA for ractopamine used as feed additive in swine.  相似文献   

3.
Improper application of antibiotic chemicals to livestock and aquaculture species may lead to the occurrence of residues in food supplies. An appropriate depletion period is needed after the administration of drugs to animals for ensuring that residues in edible tissues are below established tolerance levels. This study was conducted to determine incurred amoxicillin residues in catfish muscle following oral administration. Dosed fish were harvested after four depletion periods, and muscle fillets were analyzed for amoxicillin residues using an HPLC method with precolumn derivatization and fluorescence detection. The residue levels in fish after a 6-h depletion ranged from 40 to 64 ng/g with one exception at 297 ng/g. Average residue levels decreased to 5.4 and 2. 8 ng/g after 24- and 48-h depletions, respectively. Residue levels after a 72-h depletion decreased to below the method's limit of quantitation (1.2 ng/g). An LC-MS/MS confirmatory method was developed. Confirmation of the presence of amoxicillin was demonstrated in incurred fish samples containing residues at approximately 50-300 ng/g.  相似文献   

4.
Imidacloprid, a neonicotinic insecticide, has been used as a seed dressing (Gaucho) to protect crops against soil and aerial insects. However, French beekeepers observed abnormal behavior of bees foraging on sunflowers and suspected a link between the imidacloprid seed treatment and the observed bee syndrome. This work studies the distribution of [(14)C-imidazolidin]imidacloprid (1 mg/seed) in three stages of Gaucho-treated sunflowers grown in an outdoor lysimeter. Plants absorbed <10% of [(14)C]imidacloprid spiked on seeds, and 75% of that absorbed radioactivity was found in cotyledons. Concentrations in the upper leaves were 20 times lower than in the first leaves. From the extracted radioactivity, imidacloprid accounted for 50% and metabolites for the other 50%. Four major metabolites can be detected, in variable concentrations, among which the hydroxy- and olefin-imidacloprid have toxicities equivalent to that of imidacloprid. In pollen, concentrations of imidacloprid were 13 ng x g(-1). Thus, imidacloprid residues from Gaucho seed treatment contaminated sunflower pollen, involving the translocation of imidacloprid within the plant.  相似文献   

5.
Apples were sampled directly from orchard trees at 96, 45, and 21 days postapplication with one of three organophosphate insecticides (azinphos methyl, phosalone, or phosmet, respectively). Individual apples were prepared for analysis following one of three postharvest preparations: no preparation, rinsed with deionized water for 10-15 s, or rinsed and peeled. Azinphos methyl, phosalone, and phosmet concentrations ranged from below the level of detection to 5.26 ng/g, 94.7 to 5720 ng/g, and 0.011 to 663 ng/g in the apples that received no postharvest preparation, respectively. Although rinsed apples had lower maximum concentrations than observed in apples with no preparation, levels were not significantly lower. Concentrations of all three OP insecticides in apples that were rinsed followed by peeling, however, were much lower (below detection limits to 0.733 ng/g, azinphos methyl; 0.322-219 ng/g, phosalone; and below detection limits to 44.0 ng/g, phosmet) than observed in apples that had been rinsed alone. Rinsing and peeling of apples resulted in a 74.5-97.9% reduction in OP residues, while rinsing alone lowered mean concentrations by 13.5-28.7% relative to apples that received no postharvest preparation.  相似文献   

6.
Fipronil is a pesticide suspected of having harmful effects on honey bees at microgram per kilogram levels. Considering the lack of methodology, it thus appeared to be necessary to develop a method for the determination of the lowest amounts of fipronil and its metabolites in pollen. This paper describes a new analytical method with a limit of quantification (LOQ) of 0.1 microg/kg for a representative sample weight of 5 g. In the case of a field study, this tool was used for checking the possible existence of fipronil and/or metabolites in pollen samples, but none of them contained residues higher than the LOQ. This three-step rapid method uses liquid-solid solvent extraction with mechanical grinding, followed by liquid-liquid partitioning and Florisil solid-phase extraction for the two cleanup steps. The quantification is made by liquid chromatography with electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). Indeed, combined with an adequate sample treatment, this technique offers good sensitivity and selectivity in such a complex matrix. The method has given good recoveries of 74-104% with relative standard deviations of 5.6-18.2%.  相似文献   

7.
An analytical method has been developed for the determination of total bound and extractable residues of the nitrofuran drugs furazolidone, nitrofurazone, furaltadone, and nitrofurantoin in milk of dairy cows. The method involves overnight acid hydrolysis and simultaneous derivatization of the released side chains with 2-nitrobenzaldehyde. During hydrolysis, the bound metabolites are hydrolyzed to the side chains. After pH adjustment and solid-phase extraction cleanup, the derivatives are detected and quantitated using a liquid chromatography-tandem mass spectrometry system with an atmospheric pressure chemical ionization interface. Validation of the method is accomplished by fortifying control milk with a mixture of side chains at 1, 2, and 4 ng/g. Internal standards are added at the beginning of the procedure to compensate for matrix effects and recovery losses. Method accuracies range from 83 to 104% with coefficients of variation less than 13% for all four analytes. The limits of detection are相似文献   

8.
Four laboratories obtained 177 carbamate recovery values using a liquid chromatographic method. The average recovery of 11 carbamates (aldicarb, aldicarb sulfone, bufencarb, carbaryl, carbofuran, 3-hydroxy carbofuran, 3-keto carbofuran, methiocarb, methiocarb sulfoxide, methomyl, and oxamyl) from 14 crops was 99% with a coefficient of variation of 8% (0.03-1.8 ppm fortification levels). No statistical difference in recovery was found between oxime and phenyl carbamates, or between parent and metabolite carbamates. Average recovery of aldicarb sulfoxide was 59% due to loss in the liquid-liquid partitioning because of the polarity of this compound. A fifth laboratory contributed 34 carbamate recoveries (average 99%) on table-ready food products for 4 carbamates. Bendiocarb, dioxacarb, isoprocarb, and propoxur are also quantitatively recovered through the method. Previously reported carbamate and noncarbamate recovery data are also discussed. In the Food and Drug Administration's (FDA) analysis of 319 samples (mainly crops), 86 (27%) were found to contain residues of carbamate insecticides and/or toxic carbamate metabolites. Carbaryl and methomyl were the most common carbamate residues found on the food products excluding the aldicarb sulfone and sulfoxide residues found on potatoes. In one FDA Total Diet Program "market basket", 11 of 69 table-ready food commodities contained from 0.005 to 0.094 ppm carbamate residues. Carbaryl was the most prevalent residue. Several laboratories reported adverse effects on the determinative system when inadequately purified reagents were used.  相似文献   

9.
A multiresidue technique is presented for the extraction and quantitative gas chromatographic screening of 9 insecticides (lindane, heptachlor, aldrin, heptachlor epoxide, p,p'-DDE, dieldrin, endrin, p,p'-TDE, and p,p'-DDT) as residues in beef fat. Beef fat was fortified by adding the 9 insecticides, plus dibutyl chlorendate as internal standard, to 0.5 g portions of beef fat and blending with 2 g C18 (octadecylsilyl)-derivatized silica. The C18/fat matrix blend was fashioned into a column by adding the blend to a 10 mL syringe barrel containing 2 g activated Florisil. The insecticides were then eluted from the column with 8 mL acetonitrile, and a 2 microL portion of the acetonitrile eluate was then directly analyzed by gas chromatography with electron capture detection. Unfortified blank controls were treated similarly. The acetonitrile eluate contained all of the pesticide analytes (31.25-500 ng/g) and was free of interfering co-extractants. Correlation coefficients for the 9 extracted pesticide standard curves (linear regression analysis, n = 5) ranged from 0.9969 (+/- 0.0021) to 0.9999 (+/- 0.0001). Average relative percentage recoveries (85 +/- 3.4% to 102 +/- 5.0%, n = 25 for each insecticide), inter-assay variability (6.0 +/- 1.0% to 14.0 +/- 6.7%, n = 25 for each insecticide), and intra-assay variability (2.5-5.1% n = 5 for each insecticide) indicated that the methodology is acceptable for the extraction, determination, and screening of these residues in beef fat.  相似文献   

10.
The concentration of organochlorine insecticides/metabolites, namely, lindane, heptachlor, aldrin, p,p′-DDL, p,p′-DDD, and p,p′-DDT were determined in water samples taken from two lakes, Jalmahal and Mahalon, from June 1985 to July 1986. These lakes are contaminated with moderate to high level of residues of different insecticides. In Mahalon lake the residues were highest (6.6 μg L?1) during October 1985 whereas in Jalmahal lake they were highest (9.6 μg L?1) in September 1985. In both lakes, residues of DDT exceeded the recommended limit for water quality criteria. Lindane was found in most of the samples but in lower quantities. Aldrin was the second most common residue in these lakes.  相似文献   

11.
Rain water samples were regularly collected from three sites, namely, Netaji Nagar, Moti Nagar and Town Hall within the Delhi city area from July, 1980 to June, 1982. The pesticide residues were adsorbed on polyurethane foam coated with 0.5 % DC-200 and subsequently extracted and analyzed for DDT, HCH and their metabolites/isomers. The concentration of total DDT ranged from 0.22 to 108 μg L?1 with a mean value of 12.5 μg L?1. The samples of rain water contained varying levels of 4,4-DDT, 2,4-DDT, 4,4-DDE, and 4,4-DDD. The 4,4-DDT, 4,4-DDE and 2,4-DDT were the main components of total DDT. The range of HCH residues in rain water was from 0.08 to 43 μg L?1 with a mean of 5.3 μg L?1. The residues of HCH consisted mainly of α- and γ-isomers with traces of β and δ-isomers. The α- and γ-isomers accounted for 76 and 24% of total HCH, respectively. The concentrations of DDT and HCH in rain water were generally less than 10 μg L?1 and exceeded 10 in only 4 and 3 cases, respectively. The residues of these insecticides were generally higher during October to December. Residues of DDT were higher at Moti Nagar which is near a DDT factory. Residues of HCH were maximum at Town Hall, a commercial area of the city.  相似文献   

12.
A multiresidue technique for extraction and gas chromatographic screening of 9 insecticide (lindane, heptachlor, aldrin, heptachlor epoxide, p,p'-DDE, dieldrin, endrin, p,p'-TDE, and p,p'-DDT) residues in catfish (Ictalurus punctatus) muscle tissue is presented. The 9 insecticides, plus dibutyl chlorendate internal standard, were fortified into catfish muscle tissue (0.5 g) and blended with 2 g C18 (octadecylsilyl derivatized silica reverse-phase material). The C18/muscle tissue matrix blend was fashioned into a column by adding the blend to a 10 mL syringe barrel containing 2 g activated Florisil. The insecticides were then eluted from the column with acetonitrile (8 mL), and a portion (2 microL) of the acetonitrile eluate was then directly analyzed by gas chromatography with electron capture detection. Unfortified blank controls were treated similarly. The resultant extracts contained pesticide analytes (31.25-500 ng/g) free of interfering compounds when analyzed. Correlation coefficients for the 9 extracted pesticide standard curves (linear regression analysis, n = 5) ranged from 0.9967 (+/- 0.0018) to 0.9999 (+/- 0.0001). Average percentage recoveries (82 +/- 4.8% to 97 +/- 3.6%, n = 25 for each insecticide), interassay (5.0 +/- 2.7% to 16.9 +/- 6.5%, n = 25 for each insecticide) and intraassay (1.8 to 4.7%, n = 5 for each insecticide) variabilities were indicative of an acceptable methodology for the analysis and screening of these residues in catfish muscle tissue.  相似文献   

13.
Azinphos-methyl, phosalone, and phosmet were applied individually to separate rows of trees within a commercial apple orchard in Quebec, Canada, during the 2003 agricultural season. Apples were collected for residue analysis immediately prior to the harvesting of the remaining apples for market distribution and were prepared for analysis as both individual apples and as composites of eight individuals. Analysis of the three applied compounds, as well as five organophosphate insecticides that were not applied, was performed using gas chromatography-mass spectrometry. Azinphos-methyl, phosalone, and phosmet, which were applied, were detected in all samples analyzed at concentrations ranging from 0.004 ng/g to 2260 ng/g. Methidathion was not observed in any sample. Chlorpyrifos, diazinon, dimethoate, and malathion concentrations ranged from below method detection limits to 0.71 ng/g, and the detection frequency for these compounds ranged from 20% to 100%. Residues measured in this study were all below the Canadian maximum residue limit for apples. Variability factors ranged from 2 to 19 for all compounds observed in this study. Composite samples may not accurately reflect the extremes of exposure from consumption of single servings of apples.  相似文献   

14.
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   

15.
Sediment samples collected in 1980-1982 from riverine and pothole wetlands at 17 locations in the north central United States were analyzed for organochlorine pesticides, certain of their metabolites, and polychlorinated biphenyls (PCBs). Concentrations were above minimum detection levels (5 ng/g of organochlorines and 20 ng/g of PCBs) in less than 4% of the samples taken. Fish samples taken at 9 of these 17 locations, and analyzed for the same compounds, showed a higher frequency of detectable contaminants. The most common compound found in fish was DDE, which was found in 51% of the samples at levels up to 512 ng/g. alpha-BHC was present at concentrations of 5 to 27 ng/g in 36% of the fish samples, and DDD was found at levels of 5 to 60 ng/g in 14%. Four other compounds, DDT, dieldrin, PCB, and trans-nonachlor, were detected in fish at relatively low concentrations in less than 10% of the samples. This survey, thus, indicated little contamination by organochlorine pesticides or PCBs in the wetland habitats of this region.  相似文献   

16.
A rapid confirmatory method for monitoring chloramphenicol (CAP) residues in honey, whole milk, and eggs is presented. This method is based on the polymer monolith microextraction (PMME) technique and high-performance liquid chromatography (HPLC)-electrospray ionization mass spectrometry (MS). A poly(methacrylic acid-ethylene glycol dimethacrylate) monolithic capillary column was selected as the extraction medium. To obtain optimum extraction efficiency, several parameters related to PMME were investigated. After dissolution in 20 mM phosphate solution at pH 4.0 and centrifugation, honey, eggs, or milk samples were directly passed through the extraction tube. The LC-MS instrument was equipped with an electrospray ion source and a single quadrupole. The eluates were analyzed by LC-MS in the negative-ion mode and by monitoring a pair of isotopic ions for the target compound. The in-source collision-induced dissociation process produced confirmatory ions. The recoveries of CAP from real samples spiked at 0.1-10 ng/g (honey), 0.2-10 ng/mL (milk), and 0.2-10 ng/g (egg) were in the range of 85-102%, with relative standard deviations ranging between 2.1% and 8.9%. The limits of detection (S/N = 3) were 0.02 ng/g, 0.04 ng/mL, and 0.04 ng/g in honey, milk, and eggs, respectively. The proposed method was proved to be robust in monitoring CAP residue in honey, milk, and eggs.  相似文献   

17.
The behavior in the field and the transfer from olives to olive oil during the technological process of imidacloprid, thiacloprid, and spinosad were studied. The extraction method used was effective in extracting the analytes of interest, and no interfering peaks were detected in the chromatogram. The residue levels found in olives after treatment were 0.14, 0.04, and 0.30 mg/kg for imidacloprid, thiacloprid, and spinosad, respectively, far below the maximum residue levels (MRLs) set for these insecticides in EU. At the preharvest interval (PHI), no residue was detected for imidacloprid and thiacloprid, while spinosad showed a residue level of 0.04 mg/kg. The study of the effect of the technological process on pesticide transfer in olive oil showed that these insecticides tend to remain in the olive cake. The LC/DAD/ESI/MS method showed good performance with adequate recoveries ranging from 80 to 119% and good method limits of quantitation (LOQs) and of determination (LODs). No matrix effect was detected.  相似文献   

18.
Tetracycline (TC) specific luminescent bacterial biosensors were used in a rapid TC residue assay sensitized to meet the EU maximum residue limit (MRL) for TC residues in poultry muscle tissue (100 microg kg(-1)) by membrane-permeabilizing and chelating agents polymyxin B and EDTA. Sensitivities of 5 ng g(-1) for doxycycline, 7.5 ng g(-1) for chlortetracycline, and 25 ng g(-1) for tetracycline and oxytetracycline were reached. Except for doxycycline, the MRLs of these tetracyclines include their 4-epimer metabolites. In the biosensor assay, all four 4-epimers showed induction capacity and antimicrobial activity, and antimicrobial activity was also observed in the inhibition assay, although with lower efficiency than that of the corresponding parent compound in both assays. The biosensor assay is an inexpensive and rapid high-throughput screening method for the detection of 4-epimer TC residues along with their parent compounds.  相似文献   

19.
A new method for the detection and quantification of ethephon residues in fruit and vegetables was developed. The present study indicates that fruit and vegetables require a rapid and simple cleanup step before using gas chromatograph/mass spectrometry. The recovery and precision of the new method were evaluated by spiking the fruit and vegetable samples with 0.01-0.1 microg/g of ethephon. The amount of ethephon residue can be determined with good accuracy (recovery, 78.6-109%; coefficient variation, 2.65-6.41%), and the detection limit, defined as the amount of ethephon equivalent to three standard deviations (SD) of the noise level in observations at the baseline level of the selected ion (m/z 110), was 4 pg. The determination limit, defined as the equivalent to 8 SD of the noise level, was 11 pg. The working range was between 10 and 1000 ng/mL, and the correlation coefficient was 0.999 in the five experiments. Ethephon residues were determined between <2 and 97 ng/g in commercial pineapples from Western Japan.  相似文献   

20.
Dissipation of residues of benzoylurea insecticides teflubenzuron (TFB) and triflumuron (TFM) under field conditions was evaluated on a pear orchard in Greece. Residues were determined by UV-HPLC analysis, with a detection limit of 0.030 mg/kg for both pesticides. TFB residues in pears were found to persist for 2 weeks and decline thereafter with 48% of the initial deposit remaining 42 days after the last application. TFM residues were found to decline following first-order kinetics and with a half-life of 39(+/-7) days. Residues of both pesticides found in pears collected at harvest maturity were lower than the maximum residue limits (MRLs) set by individual countries. Dissipation of TFB and TFM in cold-stored pears was also evaluated. TFB residues were very persistent for the whole storage period, whereas TFM residues did not dissipate for 6 weeks and then showed a constant decline; 7% of the initial concentration remained at the end of the storage period of 29 weeks.  相似文献   

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