Selective magnetic solid-phase extraction of amide herbicides from fish samples coupled with ultra-high-performance liquid chromatography with tandem mass spectrometry

An efficient magnetic dummy template molecularly imprinted polymer nanocomposite was prepared using multi-walled carbon nanotubes as a support and metolachlor deschloro as a dummy template. The obtained nanocomposites were characterized using Fourier transform infrared spectroscopy, vibrating sample magnetometry, scanning electron microscopy, and transmission electron microscopy. The adsorption performance of the obtained nanocomposites was evaluated through binding experiments, including static adsorption, kinetic adsorption, and selective recognition studies. The obtained nanocomposites were successfully applied as selective sorbents for the magnetic solid-phase extraction of seven amide herbicides (alachlor, acetochlor, pretilachlor, butachlor, metolachlor, diethatyl ethyl, and dimethachlor) coupled with liquid chromatography-tandem mass spectrometry from fish samples. Under the optimized conditions, the limit of detection was 0.01–0.1 μg/kg. The obtained recoveries of the amide herbicides from the fish samples were in the range of 88.0 to 102.1% with a relative standard deviation of less than 7.5%. This method, which eliminated the effect of template leakage on qualitative and quantitative analysis was found to be superior to the methods reported in the literature. The results indicated that it could be successfully applied to analyze amide herbicides in fish samples with satisfactory recoveries.     

Evaluation of 2-hydroxyethyl methacrylate as comonomer in the preparation of water-compatible molecularly imprinted polymers for triazinic herbicides

In this work, the preparation and evaluation of water-compatible molecularly imprinted polymers for triazines using 2-hydroxyethyl methacrylate and methacrylic acid as comonomers is described. Four sets of molecularly imprinted and non-imprinted polymers for propazine were prepared at varying monomer molar ratios (from 4:0 to 1:3), and evaluated for the recognition of several triazines directly in aqueous media. The evaluation was performed by loading 1 mL of an aqueous solution containing 500 ng of each selected triazine, washing with 500 μL of acetonitrile, and eluting with 500 μL of methanol followed by 2 × 500 μL of a solution of methanol containing 10% of acetic acid. Final determinations were performed by high-performance liquid chromatography-ultraviolet detection. Improvement in molecular recognition of triazines in water was obtained on those molecularly imprinted polymers incorporating 2-hydroxyethyl methacrylate in 3:1 or 2:2 molar ratios, being the former selected as optimum providing recoveries for propazine up to 80%. A molecularly imprinted solid-phase extraction protocol was developed to ensure that triazines-selective recognition takes place inside selective binding sites in pure water media. Finally, the developed method was successfully applied to the determination of the selected triazines in environmental waters providing limits of detection from 0.16 and the 0.5 μg/L concentration range.     

Evaluation of a new method for chemical coating of aluminum wire with molecularly imprinted polymer layer. Application for the fabrication of triazines selective solid-phase microextraction fiber

A new solid-phase microextraction (SPME) fiber is fabricated through ultra violet irradiation polymerization of ametryn-molecularly imprinted polymer on the surface of anodized-silylated aluminum wire. The prepared fiber is durable with very good chemical and thermal stability which can be coupled to GC and GC/MS. The effective parameters on the fabrication and application procedures such as spraying mode, ultra violet irradiation (polymerization) time, number of sprayings and polymerizations, pH and ionic strength of sample and extraction time were optimized. This fiber shows high selectivity with great extraction capacity toward triazines. SPME and GC analysis of ametryn, prometryn, terbutryn, atrazine, simazine, propazine and cyanazine using the fabricated fiber result in the detection limits of 9, 32, 27, 43, 51, 74 and 85 ng mL⁻¹, respectively. The reliability of the prepared fiber in real samples has been investigated and proved by using spiked tap water, rice, maize and onion samples.     

An amperometric method for the detection of amitrole, glyphosate and its aminomethyl-phosphonic acid metabolite in environmental waters using passive samplers

The herbicides amitrole and glyphosate, and its metabolite aminomethyl-phosphonic acid (AMPA), in water samples have been directly analysed by high-performance liquid chromatography using an electrochemical (EC) detector. Limits of detection of 0.3 μg mL⁻¹ for glyphosate, 0.05 μg mL⁻¹ for AMPA and 0.03 μg mL⁻¹ for amitrole were comparable to those obtained by other authors using EC and also by liquid chromatography coupled to mass spectrometry, but the latter method requires derivatisation and pre-concentration of the sample whereas EC methods show similar sensitivity without the need of any derivatisation. The method was specifically designed to analyse extracts from passive samplers used for monitoring of polar herbicide residues in waters. To this purpose, three types of Empore^® disks were tested for their ability to adsorb and desorb these ionic, polar analytes. A procedure for their extraction from the membranes and reducing the interferences from other substances present in natural waters (i.e. humic acids) is described. The method is simple, does not require sophisticated equipment and is valid for the analysis and monitoring of herbicides residues using passive samplers.     

Ultrasonic solvent extraction and nonaqueous CE for the determination of herbicide residues in potatoes

In the present work we address the development of a simple and effective method for the determination of triazine herbicide residues in horticultural products by CE in nonaqueous media (NACE). Potato samples were selected as a representative matrix of such foods with a nonfatty content. Isolation of the analytes from the sample matrix was accomplished by extraction with organic solvents, assisted by ultrasound; a clean‐up step of the organic extracts was carried out with SPE, using an Oasis MCX® sorbent to retain the analytes directly from the organic medium. The detection limits achieved in spiked potatoes (1.7–4.0 μg/kg) were lower than the default value of maximum residue level (MRL) established by current EU legislation for pesticide residues in foodstuffs. The results obtained were compared with HPLC in order to evaluate the performance of the NACE procedure.     

Sensitive determination of amide herbicides in environmental water samples by a combination of solid‐phase extraction and dispersive liquid–liquid microextraction prior to GC–MS

In this paper, solid‐phase extraction (SPE) in combination with dispersive liquid–liquid microextraction (DLLME) has been developed as a sample pretreatment method with high enrichment factors for the sensitive determination of amide herbicides in water samples. In SPE–DLLME, amide herbicides were adsorbed quantitatively from a large volume of aqueous samples (100 mL) onto a multiwalled carbon nanotube adsorbent (100 mg). After elution of the target compounds from the adsorbent with acetone, the DLLME technique was performed on the resulting solution. Finally, the analytes in the extraction solvent were determined by gas chromatography–mass spectrometry. Some important extraction parameters, such as flow rate of sample, breakthrough volume, sample pH, type and volume of the elution solvent, as well as salt addition, were studied and optimized in detail. Under optimum conditions, high enrichment factors ranging from 6593 to 7873 were achieved in less than 10 min. There was linearity over the range of 0.01–10 μg/L with relative standard deviations of 2.6–8.7%. The limits of detection ranged from 0.002 to 0.006 μg/L. The proposed method was used for the analysis of water samples, and satisfactory results were achieved.     

HPLC-UV and HPLC-MSn multiresidue determination of amidosulfuron, azimsulfuron, nicosulfuron, rimsulfuron, thifensulfuron methyl, tribenuron methyl and azoxystrobin in surface waters

The paper presents a new HPLC method, with UV and MSⁿ detection, for the determination of seven pesticides, including the sulfonylurea herbicides amidosulfuron, azimsulfuron, nicosulfuron, rimsulfuron, thifensulfuron methyl, tribenuron methyl, and the fungicide azoxystrobin characterised by a methoxyacrilate structure. The methodology consists of a preconcentration/SPE (solid phase extraction) step and HPLC-UV (240 nm detection wavelength)-MSⁿ analysis. Under the optimised conditions and after a 1000/1 preconcentration factor, the limits of detection were lower than 14.5 ng L⁻¹ for UV detection and lower than 8.1 ng L⁻¹ for MS detection. The limits of quantification were lower than 48.3 ng L⁻¹ in UV detection and than 26.9 ng L⁻¹ in MSⁿ detection. The analysis of two samples, spiked with a mixture of the pesticides at threshold level concentrations, gave more than 60% recovery.     

Determination of triazine herbicides using membrane-protected carbon nanotubes solid phase membrane tip extraction prior to micro-liquid chromatography

A novel microextraction technique termed solid phase membrane tip extraction (SPMTE) was developed. Selected triazine herbicides were employed as model compounds to evaluate the extraction performance and multiwall carbon nanotubes (MWCNTs) were used as the adsorbent enclosed in SPMTE device. The SPMTE procedure was performed in semi-automated dynamic mode and several important extraction parameters were comprehensively optimized. Under the optimum extraction conditions, the method showed good linearity in the range of 1–100 μg/L, acceptable reproducibility (RSD 6–8%, n = 5), low limits of detection (0.2–0.5 μg/L), and satisfactory relative recoveries (95–101%). The SPMTE device could be regenerated and reused up to 15 analyses with no analyte carry-over effects observed. Comparison was made with commercially available solid phase extraction-molecular imprinted polymer cartridge (SPE-MIP) for triazine herbicides as the reference method. The new developed method showed comparable or even better results against reference method and is a simple, feasible, and cost effective microextraction technique.     

A Contribution to the Study of the Adsorption of s‐Triazine Herbicides on Glassy Carbon Electrodes by Differential‐Capacity Measurements

Measurements of differential capacity vs. potential have been made for a series of s‐triazine herbicides at different concentrations. In all cases the decrease in capacity was independent of the applied potential, so the adsorption is also independent of the potential. From the measurements it can be established that the adsorption follows Langmuir type isotherms. Adsorption constants were obtained for the different herbicides at 25 °C (simetryn, simazine, terburyn and prometon) as well as those to simetryn at different temperatures, from which the adsorption enthalpy of this herbicide was calculated being its value of 17.5 kJ mol^?1.