Determination of eight pesticides of varying polarity in surface waters using solid phase extraction with multiwalled carbon nanotubes and liquid chromatography-linear ion trap mass spectrometry

Microchimica Acta - We describe a MWCNT-based method for the solid-phase extraction of eight pesticides from environmental water samples. The analytes are extracted from 100 mL samples at...     

Column switching liquid chromatography and post-column photochemically fluorescence detection to determine imidacloprid and 6-chloronicotinic acid in honeybees

The determination of imidacloprid and its main metabolite (6-chloronicotinic acid) in honeybees was performed by liquid chromatography with post-column photochemical derivatisation in alkaline medium and fluorescence detection. The compounds were extracted from honeybees with acetone under ultrasound conditions prior to liquid-liquid partition with dichloromethane. The separation of extract components was performed using a 50 mm x 4.6 mm i.d. short column packed with 5 microm Aquasil C(18) using an acetonitrile:water gradient program as mobile phase. Injection of samples in 0.1 mol L(-1) H(3)PO(4)/KH(2)PO(4) buffer solution (pH 3) improved the chromatographic separation between the most polar components of matrix and the 6-chloronicotinic acid. Matrix components were removed to waste using an on-line clean-up method previously to post-column reaction. Limits of quantification were 0.3 and 5.0 microg L(-1) (corresponding to 1.2 and 20.0 microg kg(-1) in the honeybee sample) for imidacloprid and 6-chloronicotinic acid, respectively. The recovery was ranged from 80.2 to 91.7% with a relative standard deviation lower than 9.0%.     

New method for the photo-chemiluminometric determination of benzoylurea insecticides based on acetonitrile chemiluminescence

The viability of tandem photochemical reaction–chemiluminescence detection has been studied for the determination of five benzoylurea insecticides, namely, diflubenzuron, triflumuron, hexaflumuron, lufenuron and flufenoxuron. The ‘on-line’ photochemical reaction of benzoylurea pesticides provides an enhanced chemiluminescence response of the pesticides during their oxidation by potassium hexacyanoferrate(III) and sodium hydroxide, whose signal increases with the percentage of acetonitrile in the reaction medium. The determination was performed using a photoreactor consisting of a PFA (perfluoroalkoxy) tube reactor coil (5 m × 1.6-mm O.D. and 0.8-mm I.D.) and an 8-W xenon lamp. As the yield of the photoderivatization process and the chemiluminescent signals depend on the percentage of acetonitrile, the chromatographic column (a Gemini C18, Phenomenex 150 mm × 4.6 mm, 5-μm particle size) was chosen with the aim of using high percentages of this organic solvent in the mobile phase. Previous studies showed that the rate of the chemiluminescent reaction was very fast. Therefore, a modification was carried out in the detector in order to mix the analytes and reactants as near as possible to the measure cell. The optimised method was validated with respect to linearity, precision, limits of detection and quantification accuracy. Under the optimised conditions, linear working range extends three orders of magnitude with the relative standard deviation of intra-day precision below 10% and detection limits between 0.012 and 0.18 μg mL⁻¹, according to the compound. The proposed method has been successfully applied to the determination of benzoylureas in cucumber with good results. Figure     

Highly collinear three-way photoinduced spectrofluorimetric data arrays modelled with bilinear least-squares: Determination of tetracyclines in surface water samples

A new sensitive method for the determination of three tetracyclines in surface water samples (tetracycline, chlortetracycline and oxytetracycline) using highly collinear data corresponding to photochemical-induced fluorescence excitation emission matrices, modelled with three-way data arrays chemometric tools has been developed. The method involves irradiation of aqueous basic solution of antibiotics with UV light and fluorescence determination of the generated photoproducts after solid phase preconcentration (SPE) with Oasis hydrophilic lipophilic balance (HLB) cartridges. The chemometric models were built by using an eight samples calibration set and samples corresponding to both a validation set and a test set. The latter set containing unsuspected interferents. Considering this latter samples, recoveries of 101.5, 97.9 and 102.2 were obtained for the three analytes. Evaluation of constant and proportional bias and precision were made by using the elliptical joint confidence region (EJCR) test for the estimated intercept and slope.     

Determination of eight fluoroquinolones in groundwater samples with ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction prior to high-performance liquid chromatography and fluorescence detection

An ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of eight fluoroquinolones (marbofloxacin, norfloxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, oxolinic acid and nalidixic acid) in groundwater, using high-performance liquid chromatography with fluorescence detection (HPLC-FD). The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.4 mL of methanol), which increased the extraction efficiency and reduced the equilibrium time.     

Determination of Pyrethroid Insecticides in Vegetables with Liquid Chromatography Using Detection by Electrospray Mass Spectrometry

Liquid chromatography with electrospray mass spectrometry (LC-ES-MS) instrumentation equipped with a single quadrupole mass filter has been used to determine several pyrethroid insecticides (fenpropathrin, lambda-cyhalothrin, deltamethrin, fenvalerate, permethrin, tau-fluvalinate and bifenthrin). The applicability of the method to the determination of insecticides in spiked cucumber, green bean, tomato and aubergine was evaluated. Samples were extracted into dichloromethane without a clean-up step. Interferences due to the matrix effect were overcome using matrix matched standards. The limits of detection ranged from 4–8 ng mL^?1 (3 and 6 ng g^?1 in the vegetable samples), with relative standard deviations < 6.8%, using blank vegetable extract. Mean recoveries ranged from 80.1–109.8%.     

Crystal growth, structure and ferromagnetic properties of a Ce3Pt23Si11 single crystal

A high-quality single crystal of Ce₃Pt₂₃Si₁₁ has been grown using the Czochralski method. The crystal structure is presented and the chemical composition has been checked using an electron microprobe analyzer. Measurements of the electrical resistivity and magnetic susceptibility performed at low temperature show a ferromagnetic transition at T_c=0.44 K.     

Simple and rapid screening procedure for pesticides in water using SPE and HPLC/DAD detection

An HPLC method, using a photodiode array detector (DAD) has been developed for the simultaneous screening of pesticides. A solid phase extraction system (SPE) has been combined, off-line, with the HPLC/DAD to isolate, recover and quantify pesticides from water samples at ppb levels. The pesticides are eluted from a Hypersil C₁₈ column 5 μm applying a solvent elution programme with two steps, isocratic and gradient mode, in reverse phase. Full UV spectra from 200 to 400 nm are recorded on-line during the analysis and may be compared to stored spectra. The method has been applied to the determination of pesticides in real water samples.     

Simple and Rapid Determination of Benzoylphenylurea Pesticides in River Water and Vegetables by LC–ESI-MS

Liquid chromatography with electrospray mass spectrometry (LC–ESI-MS) instrumentation equipped with a single quadrupole mass filter has been used to determine several benzoylphenylurea insecticides (diflubenzuron, triflumuron, hexaflumuron, lufenuron and flufenoxuron). Chromatographic and MS parameters were optimised to obtain the best sensitivity and selectivity for all pesticides. Solid-phase extraction (SPE) using C₁₈ cartridges was applied for preconcentration of pesticide trace levels in river water samples. Recoveries of benzoylphenylurea pesticides from spiked river water (0.01 and 0.025 μg L⁻¹) were between 73 and 110% and detection limits were between 3.5 and 7.5 ng L⁻¹. The applicability of the method to the determination of benzoylphenylurea insecticides in spiked cucumber, green beans, tomatoes and aubergines was evaluated. Samples were extracted into dichloromethane without any clean-up step. The limits of detection ranged from 1.0 to 3.2 ng mL⁻¹ (0.68 and 2.13 μg kg⁻¹ in the vegetable samples). Mean recoveries ranged from 79 to 114% at spiking levels of 0.01 and 0.03 mg kg⁻¹. The method was applied to determine traces of benzoylphenylureas in both river water and vegetable samples with precision values lower than 10%. Interferences due to the matrix effect were overcome using matrix-matched standards.     

Application of solid-phase microextraction for determination of pyrethroids in groundwater using liquid chromatography with post-column photochemically induced fluorimetry derivatization and fluorescence detection

Solid-phase microextraction (SPME) is a rapid and simple analytical technique which uses coated fused-silica fibers to extract analytes from aqueous samples. This study develops a method of SPME analysis for seven pyrethroids, including fenpropathrin, lambda-cyhalothrin, deltamethrin, fenvalerate, permethrin, tau-fluvalinate and bifenthrin in groundwater samples using high performance liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection (SPME-LC-PIF-FD). To perform the SPME, a 60 microm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used for the extraction of the pesticides from groundwater samples. The main factors affecting the SPME process, such as extraction time, stirring rate, extraction temperature, pH and the desorption process were studied. The use of photochemically induced fluorescence for detection improved sensitivity and selectivity. The limits of quantification (LOQs) obtained in the matrix, with respect to EURACHEM Guidance, varied between 0.03 and 0.075 microgL(-1). Relative recoveries ranged from 92 to 109% and relative standard deviations values ranged from 2 to 9%.