Determination of parabens in environmental solid samples by ultrasonic-assisted extraction and liquid chromatography with triple quadrupole mass spectrometry.

Analysis of various p-hydroxybenzoic esters (methyl, ethyl, isopropyl, propyl, benzyl, and butylparaben) in environmental solid samples was carried out by sonication-assisted extraction in small columns (SAESC) followed by liquid chromatography with triple quadrupole mass spectrometry (MS/MS). Solid samples were placed in small glass columns and extraction performed assisted by sonication in two consecutive steps of 15 min using acetonitrile as extraction solvent. Sample extracts were evaporated under nitrogen stream to 1 ml and analysed by LC-MS/MS. Satisfactory recoveries were obtained ranging from 83% to 110% depending on the analyte. Good limits of quantification (LOQs), between 0.11 and 0.49 ng g(-1) were obtained for LC-MS/MS, making this technique suitable for the determination of parabens in environmental solid samples, particularly at trace level. The developed method was applied to the determination of target analytes in different types of soil and sediments, finding levels between LOD and 6.35 ng g(-1).

Determination of nonylphenol and nonylphenol ethoxylates in environmental solid samples by ultrasonic-assisted extraction and high performance liquid chromatography-fluorescence detection.

A simple and rapid analytical method for the determination of nonylphenol (NP) and nonylphenol ethoxylates (NPEOx) in solid environmental samples has been developed. This method combines an ultrasonic-assisted extraction procedure in small columns and an enrichment step onto C(18) solid-phase extraction cartridges prior to separation using HPLC with fluorescence detection. Method optimization was carried out using soil samples fortified at different concentration levels (from 0.1 to 100 microg/g). Under optimum conditions, 2g of soil was placed in small glass columns and extraction was performed assisted by sonication (SAESC) at 45 degrees C in two consecutive steps of 15 min using a mixture of H(2)O/MeOH (30/70). The obtained extracts were collected, loaded onto 500 mg C(18) cartridges, and analytes were eluted with 3 x 1 ml of methanol and 1 ml of acetonitrile. Finally, sample extracts were evaporated under a nitrogen stream, redissolved in 500 microl H(2)O/AcN (50/50), and passed though a 0.45 microm nylon filter before final determination by HPLC-FL. The developed procedure allowed to achieve quantitative recoveries for NP and NPEOx, and was properly validated. Finally, the method was applied to the determination of these compounds in soils and other environmental solid samples such as sediments, compost and sludge.

Determination of selected environmental contaminants in foraging honeybees.

Colony losses of honeybees have been of great concern in the last years. To explain these losses, several studies have been reported, and various factors, such as pathogens and pesticides, have been considered as possible causes. Nevertheless, organic contaminants, rather than pesticides, are continuously released to the environment, and can be intercepted by honeybees during foraging with the possible consequent damage. Azoles and organophosphorus esters have been selected in this work as environmental contaminants to be monitored in honeybees. A fast and robust method has been developed to determine these organic pollutants in honeybees. It is based on matrix solid phase dispersion (MSPD), which performs sample dispersion with extraction and clean up in the same step, followed by LC-ESI-MS/MS determination. Recoveries of the method varied between 73% and 119% and MQLs ranged from 0.8 to 4 ng g(-1). Honeybee samples from ten apiaries located in different regions were analyzed applying the developed method. Azole compounds were found at low levels, but not in all samples, while organophosphorus esters were found in most samples whatever location. Tris-(2-chloroisopropyl) phosphate, TCPP, and tributyl phosphate, TBP, were detected in all honeybees samples at levels higher than the rest of organophosphates analyzed.

Screening of environmental contaminants in honey bee wax comb using gas chromatography-high-resolution time-of-flight mass spectrometry.

This study reports an analytical approach intended to be used for investigation of non-targeted environmental contaminants and to characterize the organic pollution pattern of bee wax comb samples. The method comprises a generic extraction followed by detection with gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-TOF-MS), operated in electron impact ionization (EI) mode. The screening approach for the investigation of non-targeted contaminants consisted of initial peak detection by deconvolution and matching the first-stage mass spectra EI-MS(1) with a nominal mass spectral library. To gain further confidence in the structural characterization of the contaminants under investigation, the molecular formula of representative ions (molecular ion when present in the EI spectrum) and, for at least other two fragment ions, was provided for those with an accurate mass scoring (mass error < 5 ppm). This methodology was applied for screening environmental contaminants in 50 samples of bee wax comb. This approach has allowed the tentative identification of some GC-amenable contaminants belonging to different chemical groups, among them, phthalates and polycyclic aromatic hydrocarbons (PAHs), along with residues of veterinary treatments used in apiculture.

Multiresidue analysis of carbamate pesticides in soil by sonication-assisted extraction in small columns and liquid chromatography.

A rapid multiresidue method has been developed for the analysis of carbamate insecticides (oxamyl, methomyl, propoxur, carbofuran, carbaryl and methiocarb) in soil. The method is based on the sonication-assisted extraction of soil samples placed in small columns using a low volume of methanol. Residue levels in soil were determined by reversed-phase high-performance liquid chromatography with fluorescence detection after post-column derivatisation. The separation of carbamates is performed on a C8 column with water-methanol as mobile phase. Recovery studies were carried out at 0.5, 0.1 and 0.01 microg/g fortification levels and average recoveries obtained for carbamates ranged from 82 to 99% with relative standard deviations between 0.4 and 10%. The effect of residue residence time and soil moisture content on the insecticide recovery was also studied. The method is linear over the range assayed, from 0.1 to 1 microg/ml. The detection limit for the carbamates varied from 1.6 to 3.7 microg/kg and the quantification limit obtained was 10 microg/kg. The emission and excitation allowed the confirmation of residues at levels around 0.1 microg/g.

Determination of endosulfan isomers and endosulfan sulfate in tomato juice by matrix solid-phase dispersion and gas chromatography.

A rapid method based on matrix solid-phase dispersion was developed for the determination of endosulfan isomers and endosulfan sulfate in commercial tomato juice. After the optimisation of different parameters such as the type of adsorbent, the extraction solvent, and the extraction assistance by sonication, the recoveries obtained ranged from 81 to 100% with relative standard deviations equal to or lower than 10%. The analysis of samples was accomplished using gas chromatography with electron-capture detection and the identity of endosulfan residues was confirmed by gas chromatography-mass spectrometry with selected ion monitoring. The detection limit for these compounds, calculated as three times the background noise, was 1 microg/kg. The proposed method was applied to the analysis of these compounds in commercial juice samples and levels of endosulfan between 1 and 5 microg/kg were detected in some samples.

Multiresidue analysis of fungicides in soil by sonication-assisted extraction in small columns and gas chromatography.

A rapid multiresidue method for the simultaneous determination of 14 fungicides in soil was developed. Fungicides were exacted from soil, placed in small columns, by sonication-assisted extraction with ethyl acetate. The effect of residue residence time and soil moisture content on the fungicide recovery was studied. Residue levels in soil were determined by gas chromatography with electron-capture and nitrogen-phosphorus detection. Residue identities were confirmed by gas chromatography coupled with mass spectrometry, in the selected ion monitoring mode. Recovery studies were carried out at 0.5, 0.1 and 0.05 microg/g fortification levels for each fungicide, and average recoveries obtained for these compounds ranged from 80 to 104% with relative standard deviations between 1 and 8%. The method is linear over the range assayed, 0.5-0.05 microg/g, and the detection limit for the fungicides studied varied from 2 to 10 microg/kg.

Multiresidue analysis of insecticides in soil by gas chromatography with electron-capture detection and confirmation by gas chromatography-mass spectrometry.

A rapid multiresidue method has been developed for the analysis of nine insecticides (organochlorines, pyrethroids and organophosphorus) in soil. The method is based on the sonication extraction of residues from a certain amount of soil placed in a small column, using ethyl acetate. The effect of the residence time of insecticides in soil, the material of the columns used (glass or plastic columns) and the soil moisture content on the recovery of these compounds was also studied. Residues were determined by gas chromatography with electron-capture detection. The average recovery through the method obtained for these compounds varied from 90 to 108% with a relative standard deviation between 1 and 11%. The results of this study pointed out that the recoveries of insecticide residues obtained with plastic or glass columns at different soil moisture content were similar and that the residence of these compounds in soil during several days did not affect their recovery from soil. Confirmation of residue identity was performed by gas chromatography coupled with mass spectrometry.

Determination of herbicide residues in juice by matrix solid-phase dispersion and gas chromatography-mass spectrometry.

A rapid multiresidue method was developed for the determination of 15 herbicides in carrot, grape, and multivegetable juices. The analytical procedure was based on the matrix solid-phase dispersion of juice samples on Florisil, placed in glass columns, and subsequent extraction with ethyl acetate with assisted sonication. The recoveries through the method ranged from 82 to 115% with relative standard deviations equal or lower than 10% for all the herbicides studied. The analysis of samples was accomplished using gas chromatography-mass spectrometry with selected ion monitoring. Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. The detection limits ranged from 0.1 to 1.6 microg/l. The developed method was applied to the analysis of herbicide residues in commercial juice samples.

Determination of cereal herbicide residues in environmental samples by gas chromatography.

Gas chromatographic analysis of cereal herbicide residues in water, soil, plant and air is reviewed. Herbicides widely used in spring and winter cereals, i.e., phenoxyacids, benzonitriles, ureas, triazines, dinitroanilines, chloroacetamides and thiocarbamates, are considered. The main procedures used in the residue analysis, extraction, clean-up, derivatization and gas chromatographic determination are summarized and discussed.

Analysis of herbicide residues in cereals, fruits and vegetables.

The determination of herbicide residues in cereals, fruits and vegetables by chromatographic methods is reviewed. The principal chemical groups of herbicides, like phenoxyacids, benzonitriles, ureas, triazines, dinitroanilines, chloroacetamides, carbamates, uracils, glyphosate and bipyridylium compounds, are considered. This review briefly provides some basic information on food sample extraction, clean-up, derivatization and determination of herbicide residues.

Analysis of endosulfan isomers and endosulfan sulfate in air and tomato leaves by gas chromatography with electron-capture detection and confirmation by gas chromatography-mass spectrometry.

Rapid analytical methods for the determination of endosulfan isomers and endosulfan-sulfate in air and plant samples were developed. The insecticides were trapped from air using a column containing Florisil and extracted with a low volume of ethyl acetate, assisted by sonication. Pesticide residues were determined by gas chromatography with electron-capture detection using a nonpolar capillary column. Residue identities were confirmed by gas chromatography coupled with mass spectrometry. Recoveries of these compounds from air samples were always higher than 78% with an RSD lower than 11% and the detection limits obtained were at least 0.3 ng/l air. Leaf samples were homogenised with ethyl acetate and extracts cleaned-up on an aluminium oxide column. Pesticides were eluted with a hexane-ethyl acetate (80:20, v/v) mixture. Recoveries obtained from plant samples were higher than 78% with an RSD lower than 14% and detection limits in leaves were 0.02 microg/g for each pesticide. These methods were applied to study the volatilisation of endosulfan from tomato leaves under laboratory conditions. A volatilisation rate near 1% of the initial amount of endosulfan per hour was obtained during the first 24 h at room temperature.

Influence of soil moisture on sorption and degradation of hexazinone and simazine in soil.

Sorption and degradation rates of hexazinone and simazine on soil were determined in a sandy loam soil incubated, during 44 days, at 25 degrees C with moisture contents ranging from 4% to 18%. Herbicide levels in soil solution were also measured, after extraction of this solution by a centrifugation method. All experiments were conducted with treated soil in plastic columns, and the results showed that this method is suitable for the simultaneous study of pesticide sorption and degradation in soil at different environmental conditions. In general, sorption of both herbicides was higher for aged herbicide residues compared to recently applied herbicides, and soil subjected to drying and rewetting cycles had the highest sorption values. K(f) values ranged from 0.5 to 1.2 for simazine and from 0.2 to 0.4 for hexazinone. Degradation rates increased with soil moisture content for both herbicides, and drying-rewetting of soil yielded degradation rates slower than that obtained at 10% soil moisture content. Hexazinone concentration in soil solution decreased with incubation time faster than simazine.

Adsorption and degradation of thiazopyr in compost-amended and non-amended soils.

Adsorption and degradation of thiazopyr on two unamended soils and a soil amended annually during 8 years with compost were studied under laboratory conditions and compared with the results obtained on soils amended with fresh sewage sludge compost. The adsorption isotherms fitted the Freundlich equation well and a marked sorption increase was found in amended soils. Degradation data followed first-order kinetics and thiazopyr had a half-life of about 75 days at 25 degrees C and 60% water-holding capacity of soil. The addition of fresh compost markedly decreased the rate of thiazopyr degradation, whereas the compost mineralised in the field after annual additions had only a small influence. Incubation studies with sterile soils showed a very significant decrease of the degradation rate, indicating that degradation by micro-organisms was the main pathway of thiazopyr degradation in the soils studied.

Multiresidue determination of pesticides in honey by matrix solid-phase dispersion and gas chromatography with electron-capture detection.

A multiresidue method was developed for the determination of 15 pesticides (organochlorines, organophosphorus compounds, pyrethroids, and other acaricides) in various commercial honeys (eucalyptus, lavender, orange, rosemary, and multifloral). The analytical procedure is based on the matrix solid-phase dispersion of honey in a mixture of Florisil and anhydrous sodium sulfate; the mixture is placed in small plastic columns and extracted with hexane-ethyl acetate (90 + 10, v/v). The pesticide residues are determined by capillary gas chromatography with electron-capture detection. Recoveries with the method at concentrations between 0.15 and 1.5 microg/g ranged from 80 to 113%, and relative standard deviations were <10% for all the pesticides studied. The pesticide detection limits were within the range 0.5-5 microg/kg for organochlorines, around 3 microg/kg for the chlorinated organophosphorus pesticides studied, near 15 microg/kg for fluvalinate, and about 3 microg/kg for the other pyrethroids.

GLC analysis of thiabendazole residues in citrus fruit.

Analysis of thiabendazole (TBZ) residues in citrus fruit is performed using a bonded phase, SE-54, fused-silica capillary column. The fungicide is extracted with hexane: ethyl acetate (90:10, v/v) at high pH and, after a short cleanup, determined by gas-liquid chromatography with a nitrogen-phosphorus detector (NPD). Recoveries through the method are always higher than 80% and the limit of detection is 0.01 mg/Kg. TBZ residues are determined in whole fruit, peel, and pulp of "Washington Navel" oranges and "Hernandina" clementines treated with 1500 mg/L fungicide. Residues found in these samples and their changes during storage are reported. TBZ analysis in samples with high residue levels (peel and whole fruit) is also carried out by direct determination in the crude extracts. Results obtained with this shorter method are similar to those of the former proposed method.

Uptake of perfluorinated compounds by plants grown in nutrient solution.

The uptake rates of three perfluorinated carboxylates and three perfluorinated sufonates by a grass (B diandrus) grown in nutrient solution at two different perfluorinated compounds (PFCs) concentrations were assessed. Grass can be ingested by grazing animals causing the PFCs to enter the food chain, which is a pathway of human exposure to these compounds. A rapid and miniaturized method was developed to determine PFCs in plants, based on a matrix solid-phase dispersion (MSPD) extraction procedure followed by quantitation by HPLC-MS/MS with an MQL in the range from 1 to 9 ng/g. An increase of PFCs levels in plant was observed along the exposure time. Differences in uptake for studied perfluorinated carboxylates were found, showing a decrease with carbon chain length (from 3027 to 1,167 ng/g at the end of assay), whereas no significant differences in absorption were obtained between perfluorinated sulfonates (about 1,700 ng/g). Initially, higher PFC transfer factors (ratio between concentration in plant and concentration in initial nutrient solution) were obtained for plants growing in the nutrient solution at the highest PFC concentration, but these factors became similar with time to plants exposed to the lowest concentration.

Molecularly imprinted polymer for the extraction of parabens from environmental solid samples prior to their determination by high performance liquid chromatography-ultraviolet detection.

An analytical methodology incorporating a molecularly imprinted solid-phase extraction procedure (MISPE) has been developed for the determination of parabens in environmental solid samples. Four different polymers were prepared combining the use of acetonitrile or toluene as porogen, and 4-vinylpyridine (VP) or methacrylic acid (MAA) as monomer, using benzylparaben (BzP) as a template molecule. Although all the polymers were able to recognize the template in rebinding experiments, the MIP prepared in toluene using MAA showed better performance. This polymer was also capable of recognizing other parabens (methyl, ethyl, isopropyl, propyl, isobutyl, butyl and benzylparaben) allowing to develop an appropriated MISPE procedure for this family of compounds. The extraction of the parabens from environmental solid samples was performed by ultrasonic assisted extraction in small columns (SAESC), and this procedure next to MISPE as clean-up step followed by HPLC-UV determination was successfully used for the determination of parabens in soil and sediment samples of different locations. Recoveries ranging from 80% to 90% have been achieved depending on the compound and the samples, and limits of detection (LODs) were under 1 ng g(-1) for all the compounds, making this method suitable for the determination of parabens in environmental solid matrices. The method was further applied to the determination of paraben contents in real samples, founding levels up to 11.5 ng g(-1) in sea sediments.

Molecularly imprinted polymeric fibers for solid-phase microextraction.

Solid-phase microextraction (SPME) is widely used in analytical laboratories for the analysis of organic compounds, thanks to its simplicity and versatility. However, the current commercially available fibers are based on nonselective sorbents, making difficult in some cases the final determination of target compounds by chromatographic techniques. Molecularly imprinted polymers (MIPs) are stable polymers with selective molecular recognition abilities, provided by the template used during their synthesis. In the present work, a simple polymerization strategy allowing the obtainment of molecularly imprinted polymeric fibers to be used in SPME is proposed. Such a strategy is based on the direct synthesis of molecularly imprinted polymeric fibers (monoliths) using silica capillaries as molds, with silica being etched away after polymerization. The system propazine:methacrylic acid was used as a model for the preparation of molecularly imprinted fibers, and its ability to selectively rebind triazines was evaluated. Variables affecting polymer morphology (i.e., polymerization time, fiber thickness) and binding-elution of target analytes (i.e., solvents, time, temperature) were studied in detail. The imprinted fiber showing the best performance in terms of selectivity and affinity for triazines was successfully applied to the extraction of target analytes from environmental and food samples.

HPLC imprinted-stationary phase prepared by precipitation polymerisation for the determination of thiabendazole in fruit.

A molecularly imprinted polymer (MIP) tailored for the HPLC determination of the fungicide thiabendazole (TBZ) has been synthesised in one single preparative step by precipitation polymerisation in an acetonitrile/toluene co-solvent, using TBZ as template molecule, methacrylic acid as functional monomer and divinylbenzene-80 as crosslinker. The imprinted polymer particulates obtained were characterised by scanning electron microscopy and nitrogen sorption porosimetry. These analyses showed clearly that spherical polymer particulates (polymer microspheres) with narrow size distributions (average particle diameter approximately 3.5 microm) and well-developed pore structures had been produced. The imprinted microspheres were packed into a stainless steel HPLC column (50 x 4.6 mm id) and evaluated as an imprinted stationary phase. The imprinting effect was demonstrated clearly, i.e., the column was observed to bind TBZ selectively, and the effect of different chromatographic parameters (e.g., temperature, flow-rate and elution solvents) on TBZ retention/elution studied. Under optimised conditions, the TBZ-imprinted column was used for the HPLC-fluorescence (HPLC-F) determination of TBZ directly from orange (both whole fruit and juice), lemon, grape and strawberry extracts at low concentration levels in less than 15 min, without any need for a clean-up step in the analytical protocol.