Determination of fungicide residues in white grapes for winemaking by gas chromatography with mass spectrometric detection and assessment of matrix effects

A new analytical method, based on organic solvent extraction with dichloromethane-acetone (75 + 25, v/v) followed by gas chromatography with mass spectrometric detection, is presented for the determination of residues of 10 fungicides in white grapes for vinification. Some of them (cyprodinil, fludioxonil, and pyrimethanil) have been used for only 2-3 years and, therefore, no methods are available in the scientific literature for such a screening. Quality parameters yielded good precision (relative standard deviation of <10%) and detection limits (ranging between 1 and 18 microg/kg) that are lower than the maximum residue limits (MRLs) set by the 76/895/European Economic Community (EEC) and 90/642/EEC Directives. The applicability of the method was evaluated by analysis of 5 different white grapes produced in the Rías Baixas area in Galicia (northwestern Spain) for vinification. The method showed good performance in analyses of real samples to determine whether the concentrations of the fungicides used exceeded their MRLs. The method of standard additions was found to be necessary to avoid matrix effects in the quantification of fungicide residues. Results showed that concentrations of the fungicides identified in grapes were lower than the MRLs established by the European legislation.     

Multiresidue determination of 11 new fungicides in grapes and wines by liquid–liquid extraction/clean-up and programmable temperature vaporization injection with analyte protectants/gas chromatography/ion trap mass spectrometry

A gas chromatographic ion trap mass spectrometry (GC-ITMS) method was developed for the determination of 11 new generation fungicides (benalaxyl, benalaxyl-M, boscalid, cyazofamid, famoxadone, fenamidone, fluquinconazole, iprovalicarb, pyraclostrobin, trifloxystrobin and zoxamide) in grapes and wines. Samples were extracted with ethyl acetate:hexane (1:1, v/v) and cleaned-up with graphitized carbon black/primary secondary amine (GCB/PSA) solid-phase extraction (SPE) cartridges using acetonitrile:toluene (3:1, v/v) as eluent. The addition of analyte protectants (3-ethoxy-1,2-propanediol, d-sorbitol and l-gulonic acid γ-lactone) in the final extracts allowed to avoid the matrix-induced response enhancement effect on quantitation process with absolute recoveries ca. 100%. Precision (expressed as relative standard deviation) was lower than 16% for all fungicides. Limits of detection and quantitation were lower than 0.01 mg/kg or mg/L, except for cyazofamid, much smaller in all cases than maximum residue levels (MRLs) established by European Union for grapes and by Switzerland and Italy for wines. The proposed method was applied to determine fungicide residues in three different white grapes for vinification produced in Ribeiro area in Galicia (NW Spain), as well as in their corresponding final wines.     

Determination of fungicides in wine by mixed-mode solid phase extraction and liquid chromatography coupled to tandem mass spectrometry

A novel procedure for the determination of nine selected fungicides (metalaxyl-M, azoxystrobin, myclobutanil, flusilazole, penconazole, tebuconazole, propiconazole, diniconazole and difenoconazole) in wine samples is presented. Sample enrichment and purification is simultaneously performed using mixed-mode, anion exchange and reversed-phase, OASIS MAX solid-phase extraction (SPE) cartridges. Analytes were determined by liquid chromatography coupled to tandem mass spectrometry using atmospheric pressure electrospray ionization (LC-ESI-MS/MS). Parameters affecting the chromatographic determination and the extraction-purification processes were thoroughly investigated. Under optimized conditions, 10 mL of wine were firstly diluted 1:1 with ultrapure water and then passed through the mixed-mode SPE cartridge at a flow of ca. 5 mLmin(-1). After a washing step with 5 mL of an aqueous NH(4)OH solution (5%, w:v), analytes were recovered with just 1 mL of methanol and injected in the LC-MS/MS system without any additional purification. The selective extraction process avoided significant changes in the ionization efficiency for red and white wine extracts in comparison with pure standards in methanol. Performance of the method was good in terms of precision (RSDs<11%) and accuracy (absolute recoveries>72%, determined against pure standards in methanol) reporting method LOQs in the range of 0.01-0.79 ngmL(-1) for target compounds, which are far below the EU maxima residue levels (MRLs) for fungicides in vinification grapes and wine. Several commercial wines from different geographic areas in Spain were analyzed. In most samples, metalaxyl-M and azoxystrobin were found at concentrations up to several ngmL(-1).     

On-line preconcentration and chiral separation of propiconazole by cyclodextrin-modified micellar electrokinetic chromatography

A method for the chiral separation of propiconazole using cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) with hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD) as chiral selector is reported. The use of a mixture of 30 mM HP-gamma-CD, 50mM SDS, methanol-acetonitrile 10%:5% (v/v) in 25 mM phosphate buffer solution was able to separate two enantiomeric pairs of propiconazole. Stacking- and sweeping-CD-MEKC under neutral pH (pH 7) and under acidic condition (pH 3.0) were used as two on-line preconcentration methods to increase detection sensitivity of propiconazole. Good repeatabilities in the migration time, peak area and peak height were obtained in terms of relative standard deviation (RSD). A sensitivity enhancement factor of 100-fold was achieved using sweeping-CD-MEKC at acidic pH. This is the first report on the separation of two pairs of propiconazole enantiomers and all the enantiomers of fenbuconazole and tebuconazole using sweeping-CD-MEKC. The limit of detection (S/N=3) for the three triazole fungicides ranged from 0.09 to 0.1 microg/mL, which is well below the maximum residue limits (MRL) set by Codex Alimentarius Commission (CAC). Combination of solid-phase extraction (SPE) pretreatment and sweeping-CD-MEKC procedure was applied to the determination of selected triazole fungicides in grapes samples spiked at concentration 10-40 times lower than the MRL established by the CAC. The average recoveries of the selected fungicides in spiked grapes samples were good, ranging from 73% to 109% with RSD of 9-12% (n=3).     

Multiple pesticide analysis in wine by MEKC combined with solid-phase microextraction and sample stacking

In this work, a new method for the determination in white wines of 12 pesticides widely used in vine cultivars (namely, carbendazim, pirimicarb, metalaxyl, pyrimethanil, procymidone, nuarimol, azoxystrobin, tebufenozide, fenarimol, benalaxyl, penconazole, and tetradifon) using solid-phase microextraction (SPME) and MEKC with diode-array detection (DAD) was developed. The MEKC buffer consisted of 100 mM sodium tetraborate and 30 mM SDS at pH 8.5 with 6% v/v 1-propanol. Reversed-electrode polarity stacking mode (REPSM) was applied as on-line preconcentration strategy. In order to carry out an effective and sensitive determination of these pesticides in wine samples, an off-line SPME procedure was optimized by means of an experimental design. After studying the extraction performance of different SPME coatings, PDMS/divinylbenzene (PDMS/DVB) fibers were found the most appropriate for the extraction of most of these pesticides. Carbendazim and metalaxyl could not be extracted from wine samples. Calibration curves for extracted standards and fortified white wines were studied in order to determine the presence of a matrix effect. The combination of both preconcentration procedures (SPME and REPSM) allowed the determination of ten of these pesticides in white wines at concentrations between 0.054 and 0.113 mg/L. (i.e., levels well below the maximum residue limits (MRLs) allowed for these compounds in wine grapes). Ten homemade wines were they analyzed with the optimized method demonstrating the usefulness of the proposed procedure.     

Analysis of thiabendazole and procymidone in fruits and vegetables by capillary electrophoresis-electrospray mass spectrometry

A capillary electrophoresis-mass spectrometry method for determining procymidone and thiabendazole in apples, grapes, oranges, pears, strawberries and tomatoes is described. Separation is achieved using a buffer of formic acid-ammonium formate at pH 3.5 with 2% of methanol. Fungicide residues present in the sample are preconcentrated by both solid-phase extraction and injection of large sample volumes into the capillary by a stacking technique, to obtain lower detection limits. Ionization is performed at atmospheric pressure in an electrospray type source and detection is carried out using positive ionization and selected ion monitoring modes. The quantitation limits are 0.005 and 0.05 mg kg(-1), and the mean recoveries are 64 and 75% for thiabendazole and procymidone, respectively, with relative standard deviations below 12% (n=5). Real fruit and vegetable samples are analyzed by the proposed method showing that residues of both fungicides are frequently present.     

Determination of pyrimethanil and kresoxim-methyl in green groceries by headspace solid-phase microextraction and gas chromatography-mass spectrometry

A method for determination of trace amounts of the fungicides pyrimethanil and kresoxim-methyl in green groceries, previous headspace solid-phase microextraction (HSSPME), was developed using gas chromatography-mass spectrometry and selected ion monitoring (GC-MS, SIM). Both fungicides were extracted with a fused-silica fiber coated with 85 microm polyacrylate. The effects of pH, ionic strength, extraction and desorption times as well as the extraction temperature were studied. The linear concentration range of application was 12.5-250 ng g(-1) for both compounds, with detection limits of 1.8-2.0 ng g(-1) for pyrimethanil and 2.8-3.1 ng g(-1) for kresoxim-methyl. SPME/GC-MS analysis yielded good reproducibility (RSD between 7.4 and 15.0%). It was applied to check the eventual existence of pyrimethanil and kresoxim-methyl above the detection limits on grapes, strawberries, tomatoes and ketchup samples. The method validation was completed with spiked matrix samples. It can be applied as a monitoring tool in grapes, strawberries, tomatoes and ketchup samples.     

Capillary zone electrophoresis for the determination of thiabendazole, prochloraz and procymidone in grapes

Capillary zone electrophoresis with UV detection was applied to the simultaneous determination of thiabendazole, prochloraz and procymidone in grapes. Electrolyte conditions such as pH, composition and concentration of the buffer, addition of organic solvent and working voltage were checked to obtain a high-performance separation of the three fungicides (by measurement of separation efficiency and resolution). The most critical parameter was the pH of the running buffer. The best separation was achieved in 4 mM phosphate solution at pH 3.5. The repeatability of the migration times, expressed as RSD, was < 0.44%. The three peaks were completely resolved with a separation efficiency up to 100,000 theoretical plates. Solid-phase extraction was used for the isolation and preconcentration of the fungicides, which provided a concentration factor of 10:1 and limits of detection lower than the maximum residue limits. The mean recoveries of the fungicides were 73.75% for thiabendazole, 41.70% for prochloraz and 92.23% for procymidone. This method was used to determine these compounds in 20 real samples taken from a local market.     

Multiresidue method for the rapid determination--in grape, must and wine--of fungicides frequently used on vineyards

A rapid multiresidue gas chromatographic method for determining 17 fungicides in grapes, must and wine, widely used on vineyards, is described. A simple on-line microextraction method for isolation of fungicides was used. Nitrogen-phosphorus and electron-capture detection were used for the identification and quantitation of pesticides. For confirmation, mass spectrometic detection was used. Because of the high selectivity of both detection methods, no clean-up was necessary. The regression coefficients relating to linearity were at least 0.994. Recoveries from spiked grapes, must and wine samples ranged from 78 to 107% and relative standard deviations were not higher than 14%. Individual detection limits were in the range 0.02-0.1 ng. Limits of quantification varied from 0.01 to 0.05 mg/kg, smaller in all cases than the maximum residue limits set down by the legislations of Spain, France and Italy, the main wine-producing countries of the European Union. Only for fludioxonil and hexaconazole do the limits of quantification coincide with the maximum residue limits (0.05 mg/kg) established by the Spanish legislation.     

Determination of the fungicides vinclozolin and dicloran in soils using ultrasonic extraction coupled with solid-phase microextraction

Solid-phase microextraction (SPME) coupled to ultrasonic extraction was evaluated for extracting trace amounts of two agrochemical fungicides, vinclozolin and dicloran, in soil samples. Extraction was performed following two experimental approaches prior to the submission of the aqueous extracts to SPME-GC analysis. In the first approach, extraction involved sample homogenization with a water solution containing 5% (v/v) acetone and centrifugation prior to fiber extraction. In the second approach, the extraction of the fungicides from the soil samples was conducted using acetone as organic solvent which was then diluted with water to give a 5% (v/v) content. The pesticides were isolated with fused silica fiber coating with 85 μm polyacrylate. Parameters that affect both the extraction of the fungicides by the soil samples and the trapping of the analytes by the fiber were investigated and their impact on the SPME-GC-MS was studied. The procedures with respect to repeatability and limits of detection were evaluated by soil spiked with both analytes. Repeatability was between 5.6 and 14.2% and the limits of detection were 2-13 ng g⁻¹. The efficiency of acetone/SPME was generally better than that for water/SPME procedure showing good linearity (R²>0.99) with coefficient variations below 9%, recoveries higher than 91% and limits of detection between 2 and 3 ng g⁻¹. Finally, the recoveries obtained with acetone/SPME procedure were compared with the conventional liquid-liquid extraction using real soil samples. The acetone/SPME method was shown to be an inexpensive, fast and simple preparation method for the determination of target analytes at low nanogram per gram levels in soils.     

Determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry

Analytical methodology was developed and validated for the determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry (GC/IT-MS). Two extraction procedures were used: the first involved grapes, must, and wine extraction with alkaline cyclohexane-dichloromethane (9 + 1, v/v) solution, and the second grape extraction with acetone, dichloromethane, and petroleum ether. In both procedures, the extract was centrifuged, evaporated to dryness, and reconstituted in cyclohexane or 2,2,4-trimethylpentane-toluene (9 + 1, v/v), respectively. Spiroxamine diastereomers A and B were determined by GC/IT-MS, and a matrix effect was observed in the case of grapes but not in must and wine. Recovery of spiroxamine from fortified samples at 0.02 to 5.0 mg/kg ranged from 78-102% for grapes and must, with relative standard deviation (RSD) <13%; for red and white wines, recoveries ranged from 90 to 101% with RSD <9%. The limit of quantification was 0.02 mg/kg for grapes, must, and wine or 0.10 mg/kg for grapes, depending on the extraction procedure used.     

Occurrence of Fungicides in Vineyard and the Surrounding Environment

Seventeen fungicides were determined in different matrices from vineyard areas, including vine leaves, soils, grapes and water, using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). For leaf analysis, ultrasound-assisted extraction (UAE) was performed evaluating different solvents. UAE was compared with other extraction techniques such as vortex extraction (VE) and matrix solid-phase dispersion (MSPD). The performance of the UAE method was demonstrated on vine leaf samples and on other types of samples such as tea leaves, underlining its general suitability for leaf crops. As regards other matrices, soils were analyzed by UAE and microwave-assisted extraction (MAE), grapes by UAE and waters by SPE using cork as the sorbent. The proposed method was applied to 17 grape leaf samples in which 14 of the target fungicides were detected at concentrations up to 1000 μg g⁻¹. Furthermore, the diffusion and transport of fungicides was demonstrated not only in crops but also in environmental matrices.     

Determination of chlorpyrifos, penconazole, fenarimol, vinclozolin and metalaxyl in grapes, must and wine by on-line microextraction and gas chromatography

A rapid gas chromatographic method for determination of residue levels of one insecticide (chlorpyrifos) and four fungicides (penconazole, fenarimol, vinclozolin and metalaxyl) in grapes, must and wine is described. An on-line microextraction method was used. The matrix, once extracted with a mixture of acetone-dichloromethane (1:1, v/v) was filtered and concentrated. Electron-capture detection for chlorpyrifos, penconazole, fenarimol and vinclozolin and mass-selective detection in the selected-ion monitoring mode for metalaxyl were utilised. No clean-up was necessary because there were no interferences in the area of interest of the chromatogram. Linearity of both detectors, in the range 0.02-2 ng/microliter, was checked. In all cases, the correlation coefficient was the same or superior to 0.997. Recoveries from spiked grapes, must and wine ranged from 78% to 101% (fortification level, 0.1-1 mg/kg). Limits of determination were between 0.01 mg/kg for metalaxyl and 0.001 mg/kg for vinclozolin.     

分散固相萃取-液相色谱-串联质谱法测定谷物、蔬菜、水果中27种新型杀菌剂

建立了同时检测谷物、蔬菜和水果中27种新型杀菌剂的分散固相萃取-液相色谱-串联质谱(DSPE-LC-MS/MS)分析方法。样品经1%(体积分数)乙酸丙酮溶液提取,以无水硫酸镁(MgSO_4)脱水,经N-丙基乙二胺(PSA)、C_(18)、无水MgSO_4、多壁碳纳米管(MWCNT)混合净化剂净化,经C_(18)色谱柱分离,用乙腈和体积分数为0.1%的甲酸水溶液(含5 mmol/L乙酸铵)梯度洗脱,多反应监测(MRM)正离子模式扫描,采用外标法定量。噻呋酰胺和氯啶菌酯在20.47~200μg/kg范围内线性关系良好,其他25种新型杀菌剂在0.02~100μg/kg范围内线性关系良好,相关系数R~2≥0.995 0,加标回收率为70.02%~117.6%,相对标准偏差(RSD)为0.01%~19.62%(n=3)。噻呋酰胺和氯啶菌酯的检出限为6.15~16.67μg/kg,定量限为20.47~55.5μg/kg。其他25种新型杀菌剂的检出限为0.006~4.44μg/kg,定量限为0.02~14.79μg/kg。该方法简便、快速、可靠,可用于谷物、蔬菜、水果中27种新型杀菌剂的快速测定。     

固相萃取-气相色谱法测定茶叶中残留的92种农药

建立了茶叶中92种农药多残留的气相色谱分析方法。茶叶样品用乙腈一次性提取后,有机磷类农药经Envi-Carb固相小柱净化,用10 mL乙腈-甲苯(体积比为3∶1)洗脱剂淋洗,气相色谱-火焰光度检测器(GC-FPD)检测;有机氯类和拟除虫菊酯类农药经串联Envi-Carb和NH2固相小柱净化,用5 mL乙腈-甲苯(体积比为3∶1)洗脱剂淋洗,GC-电子捕获检测器(ECD)检测。采用外标法定量。添加回收试验的结果表明:92种农药的平均回收率为80.3%～117.1%,相对标准偏差为1.5%～9.8%。方法的检出限为0.0025～0.10 mg/kg。该方法的灵敏度、准确度和精密度均符合农药残留测定的技术要求。     

改良QuEChERS方法快速测定果蔬中8种新型琥珀酸脱氢酶抑制剂类杀菌剂

建立了一种同时测定果蔬中啶酰菌胺、吡噻菌胺、吡唑萘菌胺、氟唑菌酰胺、联苯吡菌胺、氟唑环菌胺、氟唑菌苯胺和氟吡菌酰胺8种新型琥珀酸脱氢酶抑制剂类杀菌剂残留量的液相色谱-串联质谱方法。通过比较乙二胺-N-丙基硅烷（PSA）和十八烷基键合硅胶吸附剂（C₁₈）两种分散固相萃取剂不同添加剂量下的吸附作用和净化效果,优化QuEChERS方法净化过程,以乙腈-0.1%（体积分数）甲酸水溶液为流动相进行梯度洗脱,使8种目标化合物在Poroshell 120 EC-C₁₈色谱柱上分离,经电喷雾正/负双离子扫描、多反应监测模式质谱检测,外标法定量。8种目标化合物在0.5~500.0 μg/L范围内线性关系良好,相关系数均大于0.998,方法检出限为0.2~1.7 μg/kg,定量限为0.5~5.0 μg/kg。各种目标化合物在8种基质中3个添加水平（5.0、25.0和125.0 μg/kg）下的回收率为71.4%~121.3%,相对标准偏差（RSD,n=6）为0.8%~17.2%。该方法操作简单、净化效果好,适用于果蔬中新型琥珀酸脱氢酶抑制剂类杀菌剂的快速检测。     

Simultaneous determination of thiamethoxam,clothianidin, and metazachlor residues in soil by ultrahigh performance liquid chromatography coupled to quadrupole time‐of‐flight mass spectrometry

A rapid pioneering method has been developed to simultaneously determine residues of three pesticides (thiamethoxam, clothianidin, and metazachlor) in soil by ultrahigh performance liquid chromatography coupled to a mass spectrometry detector (quadrupole time‐of‐flight). An efficient extraction procedure (90–105% average analyte recoveries) has also been proposed, involving solid–liquid extraction by a mixture of water and methanol (60:40, v/v), centrifugation, and concentration. A chromatographic analysis of the compounds was achieved in 5.5 min by means of a core–shell technology based column (Kinetex^® EVO C₁₈, 50 × 2.1 mm, 1.7 μm, 100 Å). The mobile phase (0.3 mL/min, gradient elution mode) consisted of 0.1% v/v formic acid in water and 0.1% v/v formic acid in acetonitrile. The method was fully validated in terms of selectivity, detection and quantification limits, matrix effect, linearity, trueness, and precision. Low limits of detection and quantification were obtained, ranging from 0.2 to 3.0 μg/kg, which are similar to those published in previous studies, while the absence of a significant matrix effect allowed quantification of the pesticides with standard calibration curves. The proposed method was applied for an analysis of pesticides in several soil samples from experimental fields dedicated to oilseed rape cultivars.     

高效液相色谱-串联质谱法测定葡萄中的吡效隆和赤霉素

采用高效液相色谱-串联质谱法（HPLC-MS/MS）建立了葡萄果实中吡效隆（CPPU）和赤霉素（GA3）两种植物生长调节剂残留量的定性定量分析方法。样品用0.5%甲酸水溶液和乙腈（体积比4:1）混合溶剂提取,经Strata-X固相萃取净化,使用Agilent SB-C18 色谱柱（50mm×2.1mm,1.8μm）,以0.5%甲酸水溶液-乙腈为流动相,流量0.3mL/min,采用电喷雾离子化源（ESI）多反应监测（MRM）模式下HPLC-MS/MS检测。在最佳检测条件下,得到吡效隆和赤霉素在2.0～100.0μg/L检测范围内线性关系良好,相关系数大于0.999;检出限(LOD)分别为0.3μg/L、0.5μg/L,定量限(LOQ)分别为1.0μg/L、2.0μg/L,回收率和精密度均能达到要求,表明该法准确,可用于葡萄中吡效隆和赤霉素残留量测定。     

Multiresidue determination of 19 fungicides in processed fruits and vegetables by capillary gas chromatography after gel permeation chromatography.

A gas chromatographic (GC) method was developed for simultaneous determination of 19 fungicides (chlorothalonil, vinclozolin, dichlofuanid, triadimefon, penconazole, chlozolinate, captan, procymidone, triadimenol, folpet, hexaconazole, myclobutanil, cyproconazole, propiconazole, nuarimol, captafol, iprodione, fenarimol, and bitertanol) and the acaricide tetradifon in tomato puree, peach nectar, orange juice, and canned peas. Samples were extracted with acetone, partitioned with ethyl acetate-cyclohexane (50 + 50, v/v), and cleaned using gel permeation chromatography with ethyl acetate-cyclohexane (50 + 50, v/v) as eluant. The final extract was analyzed by GC with ion trap mass spectrometry (ITMS) using a DB5 capillary column. Recoveries from fortified samples ranged from 74.6 to 99.3%, except for triadimenol and bitertanol. Quantitation limits for most analytes were between 0.005 and 0.050 mg/kg. The purified extracts were analyzed further by GC with electron capture and nitrogen phosphorus detection, and the results were compared with those obtained by ITMS.     

Pesticide analysis in rose wines by micellar electrokinetic chromatography

In this work, the determination of 11 pesticides (pirimicarb, metalaxyl, pyrimethanil, procymidone, nuarimol, azoxystrobin, tebufenozide, fenarimol, benalaxyl, penconazole, and tetradifon) in rose wines by micellar EKC (MEKC) using reversed electrode polarity stacking mode (REPSM) as online preconcentration strategy is described. The MEKC buffer consisted of 100 mM sodium tetraborate and 30 mM SDS at pH 8.5 with 6% v/v 1-propanol. A solid-phase microextraction (SPME) procedure using PDMS/divinylbenzene (PDMS/DVB) fibers was applied to extract the selected pesticides from the rose wine samples. The comparison between the calibration curves obtained from hydroalcoholic solutions (12% v/v ethanol) and from rose wines (matrix matched calibration) showed the existence of a strong matrix effect. Furthermore, a comparison with calibration curves obtained with white wine samples also showed significant differences for most of the analyzed pesticides. As a result, a matrix matched calibration was developed. Quantitative extraction from spiked wine samples was carried out in triplicate at two levels of concentration (range 0.18-6.00 mg/L). LODs between 0.040 and 0.929 mg/L were achieved, which are below the maximum residue limits (MRLs) established for wine grapes (except for pirimicarb) by the EU and Spain legislation as well as by the Codex Alimentarius. The established method - which is solvent free, cost effective, and fast - was also applied to the analysis of several homemade rose wine samples and a commercial one. Two of the selected pesticides were found in some of the analyzed samples.