[Determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry].

A method was developed for the determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The honey and royal jelly samples were treated with different preparation methods as the result of the different components. The honey sample was extracted with ethyl acetate and cleaned up with primary second amine, and the royal jelly sample was extracted with acetonitrile-water (1:1, v/v), and cleaned up with a C18 solid-phase extraction column. Finally, the extracts of the honey and royal jelly were analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode separately. External standard calibration method was used for quantification. The linearities of calibration curves of the four insecticides were good with the correlation coefficients greater than 0.99 in the range of 50-500 microg/L. The limits of the detection (LODs) of the four insecticides were in the range of 0.12- 5.0 microg/kg, and the limits of the quantification (LOQs) were in the range of 0.40-16.5 microg/kg. The recoveries of the four insecticides spiked in honey and royal jelly at three spiked levels (10, 15 and 20 microg/kg) were in the range of 78.2 -110.0%, and the relative standard deviations (RSDs) were all below 14%. The sensitivity and selectivity of this method were good with no interfering peaks. The proposed method is simple quick and effective to analyze the four insecticide residues in honey and royal jelly.

[Determination of trifluralin residue in aquatic products and edible oils by gas chromatography-negative chemical ionization mass spectrometry].

A confirmatory method was established for the determination of trifluralin residue in aquatic products and edible oils with the technique of offline disperse solid phase extraction and gas chromatography-negative chemical ionization mass spectrometry (DSPE-GC-MS/NCI). Trifluralin was extracted from aquatic products and edible oils with acetonitrile, and liquid-liquid partitioning formed by adding anhydrous magnesium sulfate followed by a simple cleanup step known as dispersive solid-phase extraction. The aliquot was analyzed by GC-MS/NCI using isotope internal standard method. The method was reliable and stable. The recoveries of trifluralin were in the range from 80% to 100% at three spiked levels of 1.0, 2.0, and 3.0 microg/kg, and the RSDs were not more than 10.3%. The linearity of method was good from 1 to 40 microg/L, and the LOD was 0.02 microg/kg. This method can be used as a conclusive evidence method for the determination of trifluralin residue in aquatic products and edible oils.

[Determination of four kinds of illegal additive residues in sprouts and source beans by high performance liquid chromatography-tandem mass spectrometry].

A reversed-phase high performance liquid chromatography coupled with tandem mass spectrometric (LC-MS/MS) method was developed for the determination of 4-chlorophenoxyacetic acid, 6-benzylaminopurine, enrofloxacin and norfloxacin residues in sprouts and source beans. The sample was extracted by acetonitrile containing 0.1% acetic acid and concentrated. The chromatographic analysis was carried out on a C18 column with methanol and 0.1% formic acid solution as the mobile phases in gradient elution program. The MS analysis was set in electrospray ionization mode and separated to two segments of positive and negative modes. The precursor ions were m/z 189.9, 226.1, 359.9 and 320.1, while the product ions for quantification were m/z 127.0, 91.2, 315.9 and 276.2 for 4-chlorophenoxyacetic acid, 6-benzylaminopurine, enrofloxacin and norfloxacin, respectively. The calibration curves showed good linearity in the range of 5 - 200 microg/L with correlation coefficients more than 0.995. The limits of detection (LODs) were 1 microg/kg and the limits of quantification (LOQs) were 5 microg/kg for the four compounds spiked in mung bean sprouts and mung beans. The recoveries of the four compounds spiked at three levels of 5.0, 10.0 and 20.0 microg/kg ranged from 70% to 91%, with the relative standard deviations (RSDs) less than 14%. The method established is accurate, sensitive, simple, and has considerable advantages in the analysis of the four kinds of illegal additive residues in sprouts and beans simultaneously.

[Fast screening ninety-six pesticides in six kinds of agricultural products by high performance liquid chromatography-quadrupole/electrostatic field orbit trap high-resolution mass spectrometry].

A high-throughput method for the determination of 96 pesticides in six kinds of agricultural products by liquid chromatography-quadrupole/electrostatic field orbit trap high-resolution mass spectrometry was developed. After extraction with 0.1% acetic acid in acetonitrile solution and concentration, dispersive solid-phase extraction was further utilized to reduce the matrix interference. The chromatographic analysis was performed on a C18 column with methanol and 5 mmol/L ammonium acetate solution as the mobile phases with a gradient elution program. The 96 pesticide residues were analyzed in switching positive and negative modes at the same time. With the optimized mass resolution, accurate mass-to-charge ratio extraction of the target pesticide compounds in full scan mode could eliminate matrix interference effectively. Two-stage threshold-triggered full mass scan mode was utilized to further improve the accuracy of qualitative analysis. The linear ranges of all the 96 pesticides were from 1 microg/L to 200 microg/L with correlation coefficients greater than 0.99. By detecting spiked samples, the detection limits were 5 microg/kg for all the residues and the recoveries were in the range of 58% - 105% with the relative standard deviations (RSDs) between 8.8% and 18.3%.

[Determination of 17 pyrethroid pesticide residues in vegetables by gas chromatography-mass spectrometry with negative chemical ionization].

A method was established for the determination of 17 pyrethroid pesticide residues in vegetables using QuEChERS (quick, easy, cheap, effective, rugged and safe) clean-up method and gas chromatography-mass spectrometry (GC-MS) with negative chemical ionization (NCI). The pyrethroid pesticides in the sample were extracted with acetonitrile. After QuEChERS clean-up with a mixture of primary secondary amine and graphitized carbon black packings, the extract was analyzed by GC-NCI-MS in selected ion monitoring (SIM) mode. An isotope internal standard of cypermethrin was employed to the quantification. The limits of quantification ranged from 0.02 to 5 microg/kg. The recoveries of the pyrethroid pesticides spiked in three different matrixes (peas, broccoli and Chinese onion green) at four spiked levels of 10, 20, 30 and 100 microg/kg were from 71.0% to 139.0%, and the relative standard deviations were less than 12.8%. This method can be used as a conclusive evidence method of the 17 pyrethroid pesticide residues in vegetables.

Determination of 17 pyrethroid residues in troublesome matrices by gas chromatography/mass spectrometry with negative chemical ionization.

An analytical method with the technique of QuEChERS (quick, easy, cheap, effective, rugged and safe) and gas chromatography (GC)/mass spectrometry (MS) in negative chemical ionization (NCI) has been developed for the determination of 17 pyrethroid pesticide residues in troublesome matrices, including garlic, onion, spring onion and chili. Pyrethroid residues were extracted with acidified acetonitrile saturated by hexane. After a modified QuEChERS clean-up step, the extract was analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode. An isotope internal standard of trans-cypermethrin-D(6) was employed for quantitation. Chromatograms of pyrethroids obtained in all these matrices were relatively clean and without obvious interference. The limits of detection (LODs) ranged from 0.02 to 6 µg kg(-1) and recovery yields were from 54.0% to 129.8% at three spiked levels (20, 40 and 60 µg kg(-1) for chili, and 10, 20 and 30 µg kg(-1) for others) in four different matrices depending on the compounds determined. The relative standard deviations (RSDs) were all below 14%. Isomerization enhancement of pyrethroids in chili extract was observed and preliminarily explained, especially for acrinathrin and deltamethrin.

[Determination of cyanuric acid in milk and milk powder by high performance liquid chromatography-tandem mass spectrometry].

A method for the determination of cyanuric acid (CYA) in milk and milk powder was developed using high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI MS/MS). The target analyte was extracted from samples by acetonitrile, and the proteins were precipitated at the same time. The supernatant was cleaned up and enriched with a strong anion exchange column, analysed by HPLC-MS/MS with an AX column, and quantified by internal standard method. Good linearity was obtained in the range of 50-2000 microg/L. The recoveries were all ranged from 97% to 121% at three levels, 200, 500 and 1000 microg/kg, and the relative standard deviations (RSDs) were all below 4.8%. Limit of quantification (LOQ) was 200 microg/kg. The method has high accuracy and precision, the operation is fast, easy and suitable for the determination of CYA in milk and milk powder.

[Determination of maleic hydrazide in vegetables by high performance ion-exclusion chromatography].

A new method was developed for the determination of maleic hydrazide (MH) in potatoes, onions and garlics by high performance ion-exclusion chromatography (HPIEC). The sample was extracted with acidic methanol, and then analyzed by HPIEC. The analytical column was IonPac ICE-AS1 (250 mm x 9 mm) and a mixture of 3 mmol/L formic acid water solution-acetonitrile (70: 30, v/v) was used as the eluent at a flow rate of 0.8 mL/min. The detection was performed at 205 nm by an Ultimate 3000 VWD. The quantitative analysis of external standard calibration curves was used. The linear range of the method for MH was 0.006 - 1.0 mg/L (r = 0.999 9). The average recoveries were 91% - 103% with relative standard deviations (RSDs) less than 3%. The detection limit was 0.002 mg/L for MH. The method is simple, effective, precise, sensitive, reproducible and selective. It can be used to determine the residue of MH in potatoes, onions and garlics.

[Determination of 107 pesticide residues in vegetables using off-line dispersive solid-phase extraction and gas chromatography-tandem mass spectrometry].

A screening method was developed for the determination of 107 pesticide residues in vegetables using off-line dispersive solid-phase extraction (DSPE) and gas chromatography-tandem mass spectrometry (GC-MS/MS). The pesticides interested were extracted from the samples with acetonitrile (saturated by n-hexane) containing 1% acetic acid and simultaneously separated by liquid-liquid partitioning with adding anhydrous magnesium sulfate plus sodium acetate following by a simple cleanup step known as dispersive solid-phase extraction. The extracts were determined by GC-MS/MS using external standard method. The method was reliable and stable that the recoveries of almost all pesticides were in the range from 60% to 130% at the spiked level of 10 microg/kg into four vegetable matrixes (garlic, green bean, radish 8 and spinach) and the relative standard deviations (RSDs) were all not more than 15.3%. The linearity of the method was good between 0.05 mg/L and 1 mg/L, and all limits of quantification (LOQs) less than 10 microg/kg. The method is selective with no interference, especially in the complicated garlic matrix.

[Determination of 20 kinds of pesticide residues in soybeans and corn using gas chromatography-negative chemical ionization mass spectrometry coupled with offline disperse solid-phase extraction].

A method was developed for the determination of 20 kinds of pesticide residues in soybeans and corn with the technique of offline disperse solid-phase extraction and gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The pesticides interested were extracted twice from the samples with acetonitrile. The combined extract was concentrated to dryness and redissolved in acetonitrile, then cleaned up by dispersive solid-phase extraction with sorbents of N-propyl ethylene diamine (PSA), graphited carbon black, and C18, and determined and confirmed by GC-NCI/MS. The recoveries of all pesticides were in the range of 70%-130% at three spiked levels (5, 10 and 20 microg/kg), and the relative standard deviations were below than 17%. The linearity of the method was good in the concentration range of 20-400 microg/L, and limits of quantification (LOQs) were no more than 2 microg/kg. The method is selective well with no interference and suitable for the confirmatory of pesticide residues in soybeans and corn.

[Simultaneous determination of 19 quinolone residues in honey using high performance liquid chromatography-tandem mass spectrometry].

A method for the simultaneous analysis of 19 quinolone residues, enrofloxacin, ciprofloxacin, norfloxacin, ofloxacin, difloxacin, oxolinic acid, flumequine, sarafloxacin, sparfloxacin, danofloxacin, fleroxacin, marbofloxacin, enofloxacin, orbifloxacin, pipemidic acid, pefloxacin, lomefloxacin, cinofloxacin, and nalidixic acid in honey was developed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). In comparison of the three different extraction methods, i.e. acid solution coupled with cation-exchange solid-phase extraction cartridge (PCX), neutral buffer solution coupled with a reversed-phase extraction cartridge (HLB) and alkali solution coupled with a strong anion-exchange solid-phase extraction cartridge (PAX), the third method was finally used. The cartridge was then applied to accumulate and purify the target analytes from the sample matrices in one step. The HPLC separation was performed on a C18 column with a linear gradient elution program of methanol and 0.1% formic acid solution as the mobile phase. Selective reaction monitoring (SRM) was used for the selective detection of 19 quinolones. The linearity of all the 19 quinolones in the range from 1 microg/L to 100 microg/L had correlation coefficient greater than 0.991. In the detection of spiked samples, the detection limit of the method was 1.0 microg/kg for all the 19 quinolones, and the recoveries were 71% - 118% with the relative standard deviations of 4.2% - 6.7%. Internal standard calibration was used for the quantitative analysis.

[Determination of 12 azole fungicide residues in beans and corn by offline disperse solid phase extraction and gas chromatography-negative chemical ionization mass spectrometry].

A confirmatory method is proposed for the determination of 12 azole fungicide residues in beans and corn with the technique of offline disperse solid phase extraction (DSPE) and gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The pesticides interested were extracted from the samples with acetonitrile containing 1% acetic acid and simultaneous liquid-liquid partitioning formed by adding anhydrous magnesium sulfate plus sodium acetate followed by a simple cleanup step known as dispersive solid-phase extraction. The aliquot was determined and confirmed by GC-NCI/MS using external standard method. The recoveries of all pesticides were between 70% and 130% at the three spiked levels, 10 microg/kg, 20 microg/kg and 40 microg/kg. The relative standard deviations were less than 13.9%. The linearity of method was good from 50 to 1 000 microg/L. The limits of quantification (LOQ) were less than 8 microg/kg. The method is selective with no interference and is suitable for the confirmatory of pesticide residues in beans and corn.

[Determination of triadimenol residue in foods with dispersive solid phase extraction cleanup by gas chromatography-negative chemical ionization mass spectrometry].

A confirmatory method is presented for the determination of triadimenol residue in foods by dispersive solid phase extraction-gas chromatography-negative chemical ionization mass spectrometry (SPE-GC-NCI/MS). Triadimenol residue was extracted from different food samples, such as snow pea, carrot, orange, bean, spinach, oolong tea, rice, beef, longsnout catfish, royel jelly, red swamp crayfish, bee honey etc with acetonitrile containing 1% acetic acid and simultaneous liquid-liquid partitioning formed by adding anhydrous magnesium sulfate plus sodium acetate, followed by a simple clean-up step known by dispersive solid-phase extraction. The aliquot was determined and confirmed by gas chromatography-negative chemical ionization mass spectrometry using external standard method. The average recoveries at the three spiked levels (0.005, 0.010 and 0.020 mg/kg) in different samples ranged from 70% to 110%, and the relative standard deviations were lower than 12.0%. The linearity of detection ranged from 0.050 to 0.750 mg/L. The detection limit of the method was 0.001 mg/kg and the limit of quantification was 0.003 mg/kg. The method is selective with no interference and suitable for confirmatory of triadimenol residue in 12 categories of foods.

[Determination of cyflufenamid residue in carrots by gas chromatography-negative chemical ionization mass spectrometry].

A method was developed for the determination of cyflufenamid residue in carrots by solid phase extraction-gas chromatography-negative chemical ionization mass spectrometry (SPE-GC-NCI/MS). Cyflufenamid residue was extracted with ethyl acetate from carrots. The extract was cleaned-up by an active carbon SPE column connected to a neutral alumina SPE column. The analysis was carried out by the GC-NCI/MS with selected ion monitoring mode. The recoveries of cyflufenamid in carrot samples were in the range from 74.9% to 94.6% at four spiked levels, 0.005, 0.01, 0.02, 0.04 mg/kg, and the relative standard deviations (RSD) were less than 9.7% for inter-days. The linearity of the method was good in the range from 10 to 1000 ng/mL, and the limit of detection (LOD) was 0.001 mg/kg, and the limit of quantitation (LOQ) was 0.005 mg/kg. The method is selective without interference and is suitable for the determination and confirmation of cyflufenamid residue in carrots.

[Determination of acetanilide herbicide residues in tea by gas chromatography-mass spectrometry with two different ionization techniques].

An analytical method of solid phase extraction-gas chromatography-mass spectrometry with two different ionization techniques was established for simultaneous determination of 12 acetanilide herbicide residues in tea-leaves. Herbicides were extracted from tea-leaf samples with ethyl acetate. The extract was cleaned-up on an active carbon SPE column connected to a Florisil SPE column. Analytical screening was determined by the technique of gas chromatography (GC)-mass spectrometry (MS) in the selected ion monitoring (SIM) mode with either electron impact ionization (EI) or negative chemical ionization (NCI). It is reliable and stable that the recoveries of all herbicides were in the range from 50% to 110% at three spiked levels, 10 microg/kg, 20 microg/kg and 40 microg/kg, and the relative standard deviations (RSDs) were no more than 10.9%. The two different ionization techniques are complementary as more ion fragmentation information can be obtained from the EI mode while more molecular ion information from the NCI mode. By comparison of the two techniques, the selectivity of NCI-SIM was much better than that of EI-SIM method. The sensitivities of the both techniques were high, the limit of quantitative (LOQ) for each herbicide was no more than 2.0 microg/kg, and the limit of detection (LOD) with NCI-SIM technique was much lower than that of EI-SIM when analyzing herbicides with several halogen atoms in the molecule.

[Determination of difenoconazole residue in foods by gas chromatography-negative chemical ionization mass spectrometry].

A method is presented for the determination of difenoconazole residue in all kinds of foods by solid phase extraction-gas chromatography-negative chemical ionization mass spectrometry (SPE-GC-MS/NCI). Difenoconazole residue was extracted with ethyl acetate from different samples, such as perilla leaves, carrots, spinach powder, rice, gram, jasmine flower tea, oolong tea, strawberries, sauce, bee honey, beef, chicken and eels, etc. The extracts were cleaned-up by active carbon SPE column connected to alumina neutral SPE column or Florisil SPE column only. Analytical screening was determined by the technique of GC-MS/NCI on selected ion monitoring mode. The recoveries of difenoconazole in most samples were in the range from 70% to 120% at three spiked levels, 0.01 mg/kg, 0.04 mg/kg and 0.10 mg/kg, and the relative standard deviations (RSDs) were below 9.5%. The linearity of the method is good from 0.02 to 1.00 mg/L, and limit of detection (LOD) was 0.000 5 or 0.001 mg/kg for different type samples. The method is selective without interference and is suitable for determination and conformation of difenoconazole residue in all kinds of foods.

[Determination of metabolites of nitrofuran antibiotics in royal jelly by high performance liquid chromatography-tandem mass spectrometry].

Nitrofurans are a group of widely used veterinary antibiotics that have been banned in many countries. This has generated a great deal of interests and demands for assay of nitrofurans in animal food products. To our knowledge, this is the first time that a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method has been successfully developed for simultaneously analyzing the metabolites of four nitrofuran antibiotics (furazolidone, furaltadone, nitrofurazone and nitrofurantoin) in royal jelly. Trichloroacetic acid solution was used both to precipitate proteins and to provide acidic reaction condition. Four isotope internal standards were utilized to improve the quantitative precision. The limits of detection (LODs) were 0.03 microg/kg for the metabolite of furaltadone and 0.05 microg/kg for the other three metabolites. The limits of quantitation were 0.20 microg/kg for the metabolite of furaltadone and 0.25 microg/kg for the other three metabolites. The linear range was 0.4-20 ng/mL for all the target analytes. The recoveries calibrated by internal standard were in the range of 97.7%-104.8 with the relative standard deviations (RSDs) of 2.7-9.7. It showed that this method could meet the requirements of national monitoring plan in China and the Minimum Required Performance Limits (MRPL) set by the European Union.

[Determination of lincosamide residues in honey using high performance liquid chromatography-electrospray tandem mass spectrometry].

An analytical method for the determination of lincosamide antibiotic residues in honey was developed. In the procedure a solid-phase extraction for the isolation of lincomycin and clindamycin from diluted honey samples was employed. The residues of lincomycin and clindamycin were subsequently analyzed by reversed-phase high performance liquid chromatography (RP-HPLC) coupled with electrospray tandem mass spectrometry. Mass spectral acquisition was applied with selective reaction monitoring of two diagnostic transition reactions. The qualitative analysis was based on the retention time, the precursor ion and two product ions, and the quantitation was carried out with intension of the characteristic ion m/z 126. The linear ranges were from 1.0 microg/L to 200 microg/L for lincomycin and clindamycin and the correlation coefficients (r2) were all greater than 0.996. The average recoveries for lincomycin and clindamycin ranged from 80% to 110% in replicate sets of honey samples spiked with the drug concentrations of 1.0, 5.0 and 20.0 microg/kg, and the relative standard deviations (RSDs) were less than 8% for intra-day and 15% for inter-day determinations. The method detection limit and quantitation limit were 0.1 micro/kg and 0.5 microg/kg, respectively. The method is simple and suitable for routine analysis.

[Determination of three nitroimidazole residues in royal jelly by high performance liquid chromatography-tandem mass spectrometry].

A method for analysis of trace metronidazole (MTZ), dimetridazole (DMZ) and ronidazole (RNZ) residues in royal jelly was developed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). After samples were dissolved in sodium hydroxide solution to disassociate target analytes from matrix, liquid-liquid extraction methods by ethyl acetate solvent were used. Matrix effects were minimized and good quantitation results were obtained by using highly-selective reaction monitoring (H-SRM) technology when deuterated dimetridazole (dimetridazole-D3) was selected as internal standard. Limits of detection (LODs) were 1.0 microg/kg for DMZ, 0.5 microg/kg for MTZ and RNZ (S/N > 5). Limits of quantitation (LOQs) were 2.0 microg/kg for DMZ, 1.0 microg/kg for MTZ and RNZ (S/N > 10). The linear ranges were 2.0 - 200 microg/L for all target analytes. Recoveries and relative standard deviations (RSDs) were in the ranges of 96.6% - 110.6% and 2.1% -7.4%, respectively. This method is suitable for statutory residue testing in the National Residue Surveillance Plan in China and meets the requirement for export.

[Determination of acrylamide in foods by gas chromatography-mass spectrometry].

A confirmatory method is presented for the determination of acrylamide in different food products by gas chromatography-mass spectrometry (GC-MS). The method is based on the extraction of acrylamide with and methanol, and purification with Carrez I zinc sulfate) and Carrez II (potassium hexacyanoferrate) solution, followed by bromination onto the acrylamide double bond. The derivative was extracted with ethyl acetate/hexane (4: 1, v/v), and converted to the stable 2-bromopropenamide by dehydrobromination using 10% triethylamine, then analyzed by GC-MS, employing 13C3-acrylamide as internal standard. In-house validation data for flour and bread showed good accuracy and precision of the method. The recoveries of acrylamide in the French fries and bread were all in the range from 80% to 110% after correction of analyte loss by the internal standard at three spike levels of 0.02, 0.05 and 0.2 mg/kg, and relative standard deviations (RSDs) no more than 12.7%. The limits of detection for flour and bread were estimated at 5 microg/kg.