Pesticides In Wine Research Articles

Novel “Green Chemistry” Analysis for Rapid Determination of Pesticides in Wine

Novel “Green Chemistry” Analysis for Rapid Determination of Pesticides in Wine

Hydrophobic Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction Applied to the Analysis of Pesticides in Wine.

A green solvent-based DLLME/HPLC-MS method for the determination of 19 pesticides in wine samples has been developed. The extractant solvent is a hydrophobic eutectic mixture composed of L-menthol and butylated hydroxytoluene in a molar ratio of 3:1. The endogenous ethanol of wine has been used as dispersive solvent, in order to avoid the solidification of the extracts under 19 °C. The mobile phase composition, the elution gradient and the sample injection volume were optimized in order to make this hydrophobic mixture compatible with conventional reversed phase chromatography and electrospray ionization. The method was validated in matrix, using a wine free from the target compounds. Average recovery as high as 80%, precision between 3 and 14%, and limits of detection and quantification much lower than the maximum residue levels (MRLs) for grapes and wines fixed by the EU regulation, make this multiresidue method fitted for the purpose, with the further advantages of being quick, cheap and in compliance with the green analytical chemistry. From the analysis of 11 commercial wines it was found that just in a bio sample the target compounds were not detectable or lower than quantification limit; as for the other samples, the most widespread and abundant pesticides were methoxyfenozide and boscalid, but their levels were much lower than the relative MRLs.

A SALTING-OUT ASSISTED LIQUID-LIQUID EXTRACTION FOR THE DETERMINATION OF TEBUCONAZOLE, CARBOFURAN AND IMIDACLOPRID IN WHITE AND ROSÉ WINES

Food safety is a constant and necessary concern due to the worldwide increase of the food demand. The monitoring of quality parameters demands the development of accurate, easy and fast procedures. The aim of this work was to develop a cheap, miniaturized and trustworthy salting-out assisted liquid-liquid extraction (SALLE) procedure for the determination of pesticides in wines. Sample and acetonitrile were mixed and the addition of NaCl and CH3COONa were used for separation of aqueous and organic phases. After centrifugation, the organic phase was directly injected into a liquid chromatograph. The developed SALLE procedure consumed at least 25-fold less reagent compared to conventional QuEChERS procedure. Additionally, the d-SPE step of the QuEChERS method was suppressed, without efficiency losses. The developed procedure was compared to the conventional methodology and no significant difference was observed. It was successfully applied to the determination of three pesticides in wines by liquid chromatography. Low consumption of sample and solvent, low residues generation, simple instrumentation are notable advantages. The suppression of the d-SPE step simplified the process and the risk of analyte losses.

Automatically High-Throughput Quantification by Paper Spray Ionization Mass Spectrometry for Multiple Pesticides in Wine

A rapid paper spray (PS) ionization tandem mass spectrometry analytical method has been developed to determine multiple pesticides in red wine. Without chromatographic separation, 36 pesticides in wine could be simultaneously determined less than 9 and 3 min, followed by off-line QuEChERS treatment and on-line paper adsorption treatment, respectively. Isotopically labeled internal standard (IS) was utilized to calibrate injection process, and linear ranges were one to three orders of magnitude for different pesticides. LODs were ranging between 0.1 and 100 ng/mL, and LOQs were ranging between 0.3 and 300 ng/mL. Method validation was used to evaluate the accuracy and precision, and the results for most analytes were at the range of 75–120%. All the data processes were automatically achieved by build-in instrument software. These methods were also compared with QuEChERS-DART-MS/MS and DART-MS/MS. The results demonstrated that PS-MS/MS was a rapid and simple method to quantify multiple pesticides in red wine.

Wpływ sorbentów „clean-up” na odzysk i efekt matrycy w wielopozostałościowej metodzie oznaczania pestycydów w winie

Wpływ sorbentów „clean-up” na odzysk i efekt matrycy w wielopozostałościowej metodzie oznaczania pestycydów w winie

Multiresidue Analysis of Pesticides in Wine and Grape Using Gas Chromatography with Microelectron Capture and Nitrogen–Phosphorus Detection

New multiresidue methods for identification and quantification of over 131 pesticides in wine and grapes have been developed. The analyses were based on gas chromatography with microelectron capture and nitrogen–phosphorus detection (GC-μECD/NPD). Two different extraction protocols (QuEChERS-citrate buffer and unbuffered methods) for wine samples were described. A full validation study of both analytical methods was carried out, including different approaches to cleanup which were evaluated: (a) extracts cleanup via dispersive solid-phase extraction (SPE), (b) the combination of simultaneous extraction with dispersive SPE and (c) extracts without cleanup. Both analytical procedures presented good performance for all analytes, with recoveries in the range of 72–113% and average relative standard deviation (RSD) ≤ 20%. Linearity was studied in the range between 0.009 and 0.023 mg/kg and showed coefficients of determination (R2) ≥ 0.99 for all pesticides. Estimated matrix effects in wine samples which were prepared with the presented methods for most compounds were < 10%. Determination of pesticide residues in grape samples was carried out by the modified QuEChERS approach. Satisfying parameters of recovery and precision at the two spiking levels (LOQ and 100 × LOQ) were achieved almost for all analytes in the range of 70–120% with RSD ≤ 20% (some exceptions were benthiavalicarb isopropyl, carbosulfan, dichlorvos, flazasulfuron, flubendiamide, mevinphos, tetrachlorvinphos and tribenuron methyl). Linearity was observed for all analytes in the concentration range of 0.002–4.158 mg/kg with coefficients of determination ≥ 0.99 except for fenpropidin. The expanded uncertainties were estimated by using a “top-down” approach as being 18% (on average) and 25% (on average) for grape and wine samples, respectively (coverage factor k = 2, confidence level 95%). Finally, the methods were applied with success to determination of pesticide residues in commercial wine and grape fruit samples.

Effect of clarification process on the removal of pesticide residues in red wine and comparison with white wine

ABSTRACTThe aim of this study was to determine the potential of seven clarifying agents to remove pesticides in red wine. The presence of pesticides in wine consists a great problem for winemakers and therefore, results on pesticide removal by clarification are very useful for taking a decision on the appropriate adsorbent. The selection of an efficient adsorbent can be based on data correlating pesticide removal in red wine to pesticides' properties, given the great number and variety of pesticides used. So, this experimental work is focused on the collection of results with regard to pesticide removal by clarification using a great number of pesticides and fining agents. A Greek red wine, fortified with single solutions and mixtures of 23 or 9 pesticides was studied. The seven fining agents, used at two concentrations, were activated carbon, bentonite, polyvinylpolypyrrolidone (PVPP), gelatin, egg albumin, isinglass-fish glue, and casein. Pesticides were selected with a wide range of properties (octanol–water partition coefficient (log Kow) 2.7–6.3 and water solubility 0.0002–142) and belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the clarified fortified wine. The correlation of the clarifying agents' effectiveness to pesticide's chemical structure and properties (log Kow, water solubility) was investigated. The antagonistic and/or synergistic effects, occurring among the pesticides in the mixtures, were calculated by indices. Pesticide removal effectiveness results of the red wine were compared to those obtained from a white wine under the same experimental conditions and discussed. The order of decreasing adsorbent effectiveness (mixture of 23 pesticides) was: activated carbon 40% > gelatin 23% > egg albumin 21% > PVPP 18% > casein 12% > bentonite 7%. Isinglass showed 12% removal at the highest permitted concentration. In the case of 9 pesticides mixture, the effectiveness was quite higher but the order remained the same compared to 23 pesticides mixture. The removal of each pesticide from its single solution was generally the highest (particularly for hydrophobic pesticides). Adsorption on fining agents is increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecules.

The Taste of Pesticides in Wines

The Taste of Pesticides in Wines

Effect of clarification process on the removal of pesticide residues in white wine

Presence of pesticides in wine is of great concern, due to their extensive use in viticulture. Seven clarifying agents (activated carbon, bentonite, polyvinylpolypyrrolidone, gelatin, egg albumin, isinglass, and casein) were examined in removing pesticides from white wine, fortified with single solutions and mixtures of pesticides. Solid phase extraction followed by GC-ECD was performed to analyse pesticide residues. The order of decreasing adsorbent effectiveness was: activated carbon 64% > egg albumin 23% ≥ gelatin 22% > PVPP 17% ≥ casein 16% > bentonite 8%. Isinglass showed 22% removal at the highest permitted concentration. The effect of the type of the clarifying agent and pesticide's chemical structure and properties (octanol-water partition coefficient and water solubility) on pesticide removal was studied. Distinct behavior is exhibited by each clarifying agent. Adsorption is increased by increasing hydrophobicity and decreasing hydrophilicity of pesticides. The removal of each pesticide from its single solution is generally higher than that from its mixtures, revealing the antagonistic and synergistic effects.

Solvent-assisted stir bar sorptive extraction by using swollen polydimethylsiloxane for enhanced recovery of polar solutes in aqueous samples: Application to aroma compounds in beer and pesticides in wine

A novel solvent-assisted stir bar sorptive extraction (SA-SBSE) technique was developed for enhanced recovery of polar solutes in aqueous samples. A conventional PDMS stir bar was swollen in several solvents with log Kow ranging from 1.0 to 3.5 while stirring for 30min prior to extraction. After extraction, thermal desorption – gas chromatography – (tandem) mass spectrometry (TD-GC-(MS/)MS) or liquid desorption – large volume injection (LD-LVI)-GC–MS were performed. An initial study involved investigation of potential solvents for SA-SBSE by weighing of the residual solvent in the swollen PDMS stir bar before and after extraction. Compared to conventional SBSE, SA-SBSE using diethyl ether, methyl isobutyl ketone, dichloromethane, diisopropyl ether and toluene provided higher recoveries from water samples for test solutes with log Kow<2.5. For SA-SBSE using dichloromethane, recoveries were improved by factors of 1.4–4.1, while maintaining or even improving the recoveries for test solutes with log Kow>2.5. The performance of the SA-SBSE method using dichloromethane, diisopropyl ether, and cyclohexane is illustrated with analyses of aroma compounds in beer and of pesticides in wine.

UHPLC/ESI-MS/MS Determination of 187 Pesticides in Wine.

This paper presents an ultra HPLC/electrospray ionization-tandem MS method to determine pesticides in wine. We adopted the quick, easy, cheap, effective, rugged, and safe (QuEChERs) method for extraction and used core-shell column to achieve ultra-HPLC to develop and validate a simple and fast method to analyze 187 pesticide residues in red and white wine samples. Pesticide residues were extracted from wine samples using QuEChERS. Ultra HPLC/electrospray ionization-tandem MS quantification was achieved using matrix-matched standard calibration curves with isotopically labeled standards or a chemical analogue as internal standards with an analytical range from 5.0 to 500.0 μg/L. The method performance characteristics that included overall recovery, intermediate precision, and measurement uncertainty were evaluated according to a nested experimental design. Generally, 98.4% (in red wine) and 96.8% (in white wine) of the pesticides had recoveries between 71 and 120%; 98.9% (in red wine) and 99.5% (in white wine) of the pesticides had the intermediate precision ≤20%; and 99.5% (in red wine) and 98.4% (in white wine) of the pesticides had measurement uncertainty ≤50%.

Determination of 27 pesticides in wine by dispersive liquid–liquid microextraction and gas chromatography–mass spectrometry

A low solvent consumption method was developed to determine 27 different classes of pesticides (including organochlorine pesticide, organophosphorus pesticide, pyrethroid pesticide, fungicide, herbicide and acaricide) in wine using dispersive liquid–liquid microextraction (DLLME). Extraction parameters including type and volume of extraction solvent, type and volume of disperser solvent, salinity, pH, centrifugation time, vortex extraction time and wine volumes were optimized. A mixture of 60μL chloroform (extraction solvent) and 940μL acetonitrile (disperser solvent) was injected into 5mL wine diluent. After shaking and centrifugation, the sedimented phase was transferred into a 200μL glass insert and determined by gas chromatography–mass spectrometry method (GC–MS). The results demonstrated that the recoveries for all the pesticides spiked at three different levels ranged from 66.7 to 126.1%. The intra-day repeatabilities (RSDs) ranged from 2.0 to 27.2%. The limits of detection ranged from 0.025 to 0.88μg/L, and the limits of quantification ranged from 0.082 to 2.94μg/L. The proposed method is very low cost, rapid and convenient, and could be an effective method for monitoring of multi-pesticide in wine.

Wide-scope screening and quantification of 50 pesticides in wine by liquid chromatography/quadrupole time-of-flight mass spectrometry combined with liquid chromatography/quadrupole linear ion trap mass spectrometry

In this paper, a wide scope screening method of pesticides in wine was established using liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF MS) and liquid chromatography/quadrupole linear ion trap mass spectrometry (LC-QqLIT MS). Information dependent acquisition (IDA) experiments are used to obtain both MS and MS/MS information for LC-QTOF MS analysis. For LC-QqLIT MS analysis, MS/MS spectra of target pesticides were simultaneously acquired using Enhanced Product Ion (EPI) mode at very low concentrations to increase the confidence in analytical results of multiple reaction monitoring (MRM) by library searching. Method validation was carried out using 50 pesticides commonly used in vineyards. The LOQs, linearity, repeatability were determined and good enough for quantification. The screening and quantification results obtained using LC-QTOF MS and LC-QqLIT MS were compared. Contaminants were screened against libraries containing over 2800 compounds based on accurate mass, isotopic patterns, and MS/MS spectra searching to extend the scope of this methodology to non-target screening.

Rapid determination of multiclass fungicides in wine by low-temperature plasma (LTP) ambient ionization mass spectrometry

LTP-MS/MS is a rapid method for the qualitative and semi-quantitative determination of pesticides in wines.

Reducing pesticide level in wine by selective filtration

Wine Pesticide residues, even when below grape regulatory limit, are a concern for consumers and have an impact on the export potential of wine in certain markets. A consortium of European SMEs (www.adfimax.com) has developed a product that reduces the level of mycotoxins and pesticides in wine while keeping all other wine parameter identical. The product is derived from renewable vegetable fiber. The production process includes both activation and micronisation. The usage recommendation is to substitute only the pre-coat, typically perlite, by the product at 1 or 1.5 kg⋅m−2 without changing the other layer (body feed) typically kieselguhr . This paper describes the results of numerous industrial trials that were performed in France, Luxemburg, Germany and Spain. The impact of the product on the wine oenological characteristics was evaluated for different wine (white, red and rose ) in different countries and for different grape variety (including Cabernet sauvignon, Merlot and Gamay). Results showed a reduction of the test wine pesticide level of 50% to 60% for all pesticides compared to the blank. Level of pesticide analyzed in the cake where extremely high at a level of a 1,000 times greater than the filtered wine showing the ability of the product to selectively capture the pesticides molecules.

Dispersive suspended microextraction

A novel sample pre-treatment technique termed dispersive suspended microextraction (DSME) coupled with gas chromatography-flame photometric detection (GC-FPD) has been developed for the determination of eight organophosphorus pesticides (ethoprophos, malathion, chlorpyrifos, isocarbophos, methidathion, fenamiphos, profenofos, triazophos) in aqueous samples. In this method, both extraction and two phases’ separation process were performed by the assistance of magnetic stirring. After separating the two phases, 1 μL of the suspended phase was injected into GC for further instrument analysis. Varieties of experiment factors which could affect the experiment results were optimized and the following were selected: 12.0 μL p-xylene was selected as extraction solvent, extraction speed was 1200 rpm, extraction time was 30 s, the restoration speed was 800 rpm, the restoration time was 8 min, and no salt was added. Under the optimum conditions, limits of detections (LODs) varied between 0.01 and 0.05 μg L −1. The relative standard deviation (RSDs, n = 6) ranged from 4.6% to 12.1%. The linearity was obtained by five points in the concentration range of 0.1–100.0 μg L −1. Correlation coefficients ( r) varied from 0.9964 to 0.9995. The enrichment factors (EFs) were between 206 and 243. In the final experiment, the developed method has been successfully applied to the determination of organophosphorus pesticides in wine and tap water samples and the obtained recoveries were between 83.8% and 101.3%. Compared with other pre-treatment methods, DSME has its own features and could achieve satisfied results for the analysis of trace components in complicated matrices.

Multiresidue determination of 160 pesticides in wines employing mixed-mode dispersive-solid phase extraction and gas chromatography–tandem mass spectrometry

A new multiresidue method for the efficient screening, identification and quantification of over 160 pesticides belonging to different chemical classes in red, rose and white wines have been developed. The analysis was based on gas chromatographic-tandem quadrupole mass spectrometric determination (GC-QqQ–MS/MS). An optimization strategy involved the selection of buffering conditions and sorbents for dispersive-solid phase extraction (dispersive-SPE) in order to achieve acceptably high recoveries and reduce co-extractives in the final extracts. As a result, the optimized procedure allowed us to obtain consistent recoveries of the target pesticides including problematic ones such as captan, chlorothalonil, dichlofluanid, folpet and tolylfluanid. The attained recoveries were typically between 80 and 110% (89% on average) with RSD values typically lower than 10% (8% on average) at three spiking levels of 0.01, 0.05 and 0.2mgkg−1. Linearity was studied in the range between 0.005 and 0.2mgkg−1 using pesticide standards prepared both in pure solvent and in the presence of matrix, showing coefficients of determination (R2) higher than 0.99 for all the pesticides except for desmedipham, thiabendazole and thiamethoxam in pure solvent. The study of the ratio of the slopes obtained in solvent and in matrix provided information about the matrix effects, which was <10%, 10–20% and >20% for 33, 36 and 31% of the studied pesticides, respectively. To improve accuracy, matrix matched standards were always used for calculation of the quantification results. The expanded uncertainties were estimated by using a “top-down” approach as being 17% on average (coverage factor k=2, confidence level 95%). Finally, the method was used with success to detect and quantify pesticide residues in commercial wines.

Low-Level Determination of Organochlorine Pesticides in Wines by Automatic Preconcentration and GC–MS–MS Detection

Solid-phase extraction using automated equipment has been applied to different types of wine (red, white, sparkling and rose) spiked with 16 organochlorine pesticides (OCPs) for their preconcentration. PRPS, Oasis HLB, Hysphere Resin SH, Resin GP, C8 and C18 sorbent cartridges were tested. The separation–detection step was carried out by gas chromatography–tandem mass spectrometry. Changes in both the volume flushed through the sorbent (ranging between 25 and 100 mL) and the volume injected into the chromatograph (1 or 10 μL) allow the detection limits of the method to be adapted to the analytes contents in the target samples. Preconcentrating 100 mL of wine and injecting into the chromatrograph 10 μL of extract, limits of detection obtained for the OPCs range between 1.7 and 9.7 ng L−1, depending on the OCP and type of wine.

Evaluation of Immunoassays as an Alternative for the Rapid Determination of Pesticides in Wine and Grape Samples

The main objective of this paper is to address the performance of immunochemical assays for the detection of the residues of three pesticides [atrazine, bromopropylate, and 2,4,6-trichlorophenol (TCP)] in real winery samples, such as wine, grapes, and grape juice. Different approaches have been evaluated to minimize interferences from the matrixes, and suitable working protocols have been established in order to achieve the necessary LODs, accuracy, and precision for real samples. A simple dilution of the sample proved to be sufficient for the determination of atrazine and bromopropylate in red and white wine and grape juice at the required levels of concentration. However, for TCP, an SPE procedure has been optimized using amino cartridges. The recoveries were above 85% in all cases, and the LOD values were below the parts per billion level, except for bromopropylate, which ranged between 2 and 50 microg/L, depending on the matrix. The grape matrix effect could be resolved by a simple extraction with methanol. Complete recoveries were obtained, and the final measurement procedures were able to determine selected pesticides below their maximum residue levels. The newly developed methods have been compared with standard chromatographic methods.

Determination of multi-class pesticides in wines by solid-phase extraction and liquid chromatography-tandem mass spectrometry

This work reports a new sensitive multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for detection, confirmation and quantification of forty-six pesticides and transformation products belonging to different chemical classes in wines. The proposed method makes use of a solid-phase extraction (SPE) procedure with Oasis HLB cartridges that combines isolation of the pesticides and sample clean-up in a single step. Analysis is performed by liquid chromatography-electrospray ionisation-tandem mass spectrometry (LC-MS/MS) operated in the selected reaction monitoring (SRM) mode, acquiring two specific precursor-product ion transitions per target compound. An investigation of matrix effects has been performed during method validation showing medium to low effects for the majority of the compounds. Limits of detection (LODs) were in the range 0.0003–0.003 mg L −1 and limits of quantification (LOQs) were in the range 0.001–0.01 mg L −1. The average recoveries, measured at two concentration levels (0.010 and 0.050 mg L −1), were in the range 70–110% for most of the compounds tested with % relative standard deviations below 20%, while a value of 0.010 mg L −1 has been established as the method limit of quantification (MLOQ) for all target species. Expanded uncertainty values were in the range 10–40% while the Horrat ratios were below 1. The method has been successfully applied to the analysis of 60 wine samples in the course of an annual monitoring study with carbendazim-benomyl, thiophanate-methyl and carbaryl being the most frequently determined pesticides.