Contributions to the ethyl acetate application in residue analysis

Summary For the determination of pesticide residues 10 fruit and vegetable samples and 2 wheat samples with unknown spray history were extracted by the micro on-line extraction technique using the binary solvent system water + ethyl acetate as the extracting agent. The results of this proposed micro extraction were compared with already tested methods and it was found that the micro ethyl acetate method was equally effective. The reduction of solvents and chemical waste by miniaturization of analytical procedures is an important step for environmental protection.     

Evaluation of Extraction Procedures of Organochlorine Pesticides from Natural Waters and Sediments

Abstract

This study aims to evaluate different procedures for the extraction of organochlorine pesticides (OCP's) from natural waters and sediments. In the case of extraction from water, a C18 disk solid-phase extraction method was employed. Recovery experiments in the range of 40 to 200 ng/l with selected organochlorine compounds resulted in average recoveries between 80 and 100%. Four different solvents, hexane, ethyl acetate, acetonitrile and methanol, were tested as eluting agents. Best recoveries were obtained with ethyl acetate and hexane. A comparative study of OCP sediment extraction procedures was performed employing sonication, Soxhlet extraction and shake-flask methods. The capacity of these methods to recover OCP's from a sediment sample fortified at 50 ng/g was evaluated using hexane : acetone (1:1 v/v), hexane: acetone (8:2 v/v), acetonitrile and dichlorometane. The three extraction techniques gave similar results and dichloromethane was the most effective solvent. The optimised methods were applied in the analysis of waters and sediments from the “Aiguamolls de l'Empordà” Nature Park, Girona (Spain).     

The extraction of iridium and platinum from organic solvents by polyurethane foam

The feasibility of extracting iridium and platinum from organic solvents onto polyurethane foam was studied. Distribution ratios obtained were 1.1 x 10(4) for the extraction of iridium from ethyl acetate, 225 for the extraction of iridium from acetone and 4.8 x 1O(3) for the extraction of platinum from ethyl acetate. Capacities of about 16% w/w were obtained for extraction of iridium from ethyl acetate, and about 2.4% for extraction from acetone.     

Determination of Aminobenzoic Acids by Extraction with a Hydrophilic Solvent Followed by the Non-Aqueous Titration of the Concentrate

The extraction of aminobenzoic acids with hydrophilic solvents (butyl alcohols, acetone, ethyl acetate) from aqueous solutions was studied. Extraction conditions were optimized using methods of experimental design. A method was developed for the selective determination of acids with the non-aqueous titration of the extract.     

Comparison of an acetonitrile extraction/partitioning and "dispersive solid-phase extraction" method with classical multi-residue methods for the extraction of herbicide residues in barley samples

An acetonitrile/partitioning extraction and "dispersive solid-phase extraction (SPE)" method that provides high quality results with a minimum number of steps and a low solvent and glassware consumption was published in 2003. This method, suitable for the analysis of multiple classes of pesticide residues in foods, has been given an acronymic name, QuEChERS, that reflects its major advantages (quick, easy, cheap, effective, rugged, safe). In this work, QuEChERS method, which was originally created for vegetable samples with a high amount of water, was modified to optimise the extraction of a wide range of herbicides in barley. Then, it was compared with known conventional multi-residue extraction procedures such as the Luke method, which was simplified and shortened by eliminating the Florisil clean-up (mini Luke) and the ethyl acetate extraction, which involves a subsequent clean-up by gel permeation chromatography (GPC) and which is the official extraction method used by some of European authorities. Finally, a simple acetone extraction was carried out to check the differences with the other three methods. Extracts were analysed by gas chromatography-time-of-flight mass spectrometry (GC-TOF/MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Mini Luke was significantly more effective for the extraction of non-polar and medium-polar compounds, but the best recoveries for polar compounds were achieved by QuEChERS and ethyl acetate methods. QuEChERS was the only method that provided an overall recovery value of 60-70% for non-, medium- and polar compounds, with some exceptions due to co-eluted matrix interferences. Clean-up by dispersive SPE was effective and did not differ so much with ethyl acetate extracts considering that QuEChERS clean-up step is much easier and less time-consuming. As a conclusion, it resulted to be the most universal extraction method by providing a well-defined phase separation without dilution and achieving acceptable recoveries in average including the extraction of the always difficult acidic herbicides. However, recoveries were not as good as required for validation purposes suggesting that residues are prone to strong matrix interactions in dry samples as barley and further method adaptation incrementing solvent strength, extraction time or more acidic or basic conditions is needed in order to achieve a complete extraction.     

多壁纳米碳管固相萃取测定水中的有机氯农药

对于水样中的有机氯农药的净化方法主要是采用传统的液液分配的方法,缺点是溶剂使用量和前处理复杂。近年来固相萃取及固相微萃取等技术被应用到水样中的有机污染物的测定。如利用键合在硅胶上的非极性(C18,LC18等)或极性物质(LC-CN,LC-NH2)对水中有机物进行富集,用GDX或XAD自填的固相柱的报道也很多。纳米技术和纳米材料的发展为开发固相萃取材料带来新契机。纳米材料是指尺寸大小在从1～100m之间物质。与普通的块体材料相比,纳米材料具有较大的比表面,因而有可能具有较大吸附容量。纳米材料在环境有机污染物分离富集方面的应用研究才刚刚开始。本文主要就纳米碳管对水样中的有机氯农药进行研究,优化固相萃取条件。     

Quantitative determination of sulfonamide residues in foods of animal origin by high-performance liquid chromatography with fluorescence detection

An HPLC method with fluorescence detection is proposed for the quantitative determination of residues of ten of the most used sulfonamides as their derivatives. Sulfonamides were isolated from meat, mix meat and kidney with ethyl acetate (first extraction) and acetone (second extraction) and further purified by partitioning three times with water-methylene chloride. The recovery for mix meat spiked with 1, 5 and 10 microg/kg of sulfonamides averaged 64%, 68% and 75%, respectively. Limits of quantitation were 1 microg/kg for sulfaquinoxaline and 0.5 microg/kg for the remaining sulfonamides.     

Effective protein extraction protocol for proteomics studies of Jerusalem artichoke leaves

Protein extraction is a crucial step for proteomics studies. To establish an effective protein extraction protocol suitable for two‐dimensional electrophoresis (2DE) analysis in Jerusalem artichoke (Helianthus tuberosus L.), three different protein extraction methods—trichloroacetic acid/acetone, Mg/NP‐40, and phenol/ammonium acetate—were evaluated using Jerusalem artichoke leaves as source materials. Of the three methods, trichloroacetic acid/acetone yielded the best protein separation pattern and highest number of protein spots in 2DE analysis. Proteins highly abundant in leaves, such as Rubisco, are typically problematic during leaf 2DE analysis, however, and this disadvantage was evident using trichloroacetic acid/acetone. To reduce the influence of abundant proteins on the detection of low‐abundance proteins, we optimized the trichloroacetic acid/acetone method by incorporating a PEG fractionation approach. After optimization, 363 additional (36.2%) protein spots were detected on the 2DE gel. Our results suggest that trichloroacetic acid/acetone method is a better protein extraction technique than Mg/NP‐40 and phenol/ammonium acetate in Jerusalem artichoke leaf 2DE analysis, and that trichloroacetic acid/acetone method combined with PEG fractionation procedure is the most effective approach for leaf 2DE analysis of Jerusalem artichoke.     

Selective Determination of Chlorobenzoic Acids Using Extraction with Hydrophylic Solvents

The extraction of 4-chlorobenzoic and 2,4-dichlorobenzoic acids with hydrophilic solvents (butyl alcohols, acetone, and ethyl acetate) from aqueous solutions was studied. Extraction conditions were optimized using mathematical methods of experimental design. A procedure was developed for the selective determination of acids using the non-aqueous titration of the extract.     

Analysis of 28 insecticides in curry leaves (Murraya koenigii L.) by gas chromatography and gas chromatography–mass spectrometry

A simple and efficient method was developed for analysis of 28 insecticides (organochlorines, organophosphates and synthetic pyrethroids) in curry leaves (Murraya koenigii L.). The extraction of the analytes was carried out with acidified acetonitrile and purification with magnesium sulphate, primary secondary amine along with graphitised carbon black to remove excess chlorophyll content in curry leaves. Acetonitrile extracts were changed into hexane + acetone (9 + 1) and hexane + toluene (9 + 1) in the final step. In another method ethyl acetate was used for extraction and purification was carried out as above. The analytes in the samples were determined by gas chromatography (GC) and confirmed by gas chromatography–mass spectrometry (GC–MS). Use of ethyl acetate increased the recovery of the analytes, but co-extractive interference led to higher GC maintenance. Acidified acetonitrile was found to be a better extraction solvent compared with ethyl acetate. The use of hexane:toluene (9:1) as exchange solvent increased the recovery of organochlorine insecticides compared with hexane:acetone (9:1). The limit of quantification (LOQ) of the method was 0.01 mg kg^?1 for organochlorine insecticides and 0.05 mg kg^?1 for organophosphates and synthetic pyrethroids. The recoveries of organochlorines were within 70.36–82.45%; organophosphates, 82.54–90.93% and synthetic pyrethroids, 88.45–90.71% at the LOQ level. The method developed was found suitable for analysis of real samples of curry leaves. The pesticides detected in curry leaves collected from the retail market were mainly organophosphates and synthetic pyrethroids.     

Microwave-assisted extraction versus Soxhlet extraction in the analysis of 21 organochlorine pesticides in plants

A method to determine 21 organochlorine pesticides in vegetation samples using microwave-assisted extraction (MAE) is described and compared with Soxhlet extraction. Samples were extracted with hexane–acetone (1:1, v/v) and the extracts were cleaned using solid-phase extraction with Florisil and alumine as adsorbents. Pesticides were eluted with hexane–ethyl acetate (80:20, v/v) and determined by gas chromatography and electron-capture detection. Recoveries obtained (75.5–132.7% for Soxhlet extraction and 81.5–108.4% for MAE) show that both methods are suitable for the determination of chlorinated pesticides in vegetation samples. The method using microwave energy was applied to grass samples from parks of A Coruña (N.W. Spain) and to vegetation from the contaminated industrial area of Torneiros (Pontevedra, N.W. Spain).     

Effective Extraction of Limonene and Hibaene from Hinoki (Chamaecyparis obtusa) Using Ionic Liquid and Deep Eutectic Solvent

The essential oils of hinoki (Chamaecyparis obtusa) leaves have anti-bacterial, anti-fungal, and relaxation properties that are likely associated with the major components such as sabinene, α-terpinyl acetate, limonene, elemol, myrcene, and hibaene. The present study describes the use of a cellulose-dissolving ionic liquid (IL) [C₂mim][(MeO)(H)PO₂] and low-toxicity solvents called betaine-based deep eutectic solvents (DESs) for the efficient extraction of hinoki essential oils. As a control method, organic solvent extraction was performed using either hexane, ethyl acetate (EtOAc), or acetone at 30 °C for 1 h. Both the experimental and control methods were conducted under the same conditions, which relied on partial dissolution of the leaves using the IL and DESs before partitioning the hinoki oils into the organic solvent for analysis. Quantitative analysis was performed using gas chromatography–mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The results indicated that extraction using the [C₂mim][(MeO)(H)PO₂]/acetone bilayer system improved the yields of limonene and hibaene, 1.5- and 1.9-fold, respectively, when compared with the control method. In addition, extraction using betaine/l-lactic acid (molar ratio 1:1) gave the greatest yields for both limonene and hibaene, 1.3-fold and 1.5-fold greater, respectively, than when using an organic solvent. These results demonstrate the effective extraction of essential oils from plant leaves under conditions milder than those needed for the conventional method. The less toxic and environmentally begin DESs for the extraction are also applicable to the food and cosmetic industries.     

Fractionation of apple procyanidins according to their degree of polymerization by normal-phase high-performance liquid chromatography

A new method was developed for the fractionation of procyanidin oligomers according to their degree of polymerization. Monomeric flavan-3-ols and low molecular mass procyanidins were selectively extracted from the lyophilized powder of apple condensed tannins (ACTs) by methyl acetate extraction. Sequentially, the separation of each oligomer from dimer to pentamer in this extract was carried out by normal-phase high-performance liquid chromatography using a silica-beads packed column. The best separation was achieved with a mobile phase system containing hexane; (1) hexane–methanol–ethyl acetate, (2) hexane–acetone. These sequential treatments can be easily adapted to large-scale fractionation.     

Analysis of Dns-amino acids by liquid chromatography. I. Selection of optimum mobile phase composition for separation of Dns-amino acids on polyvinyl acetate gel.

The separation of a mixture of ten Dns-amino acids (Gns-Gly, -Ala, -Val, -Leu, -Pro, -Hypro, -Met, -Ser, -Asn and -Gln) was carried out by liquid chromatography by using macroreticular polyvinyl acetate gel as a packing material. Different mobile phase systems were investigated, based mainly on mixtures of n-hexane with ethanol, methanol, chloroform, acetone, methyl ethyl ketone, ethyl acetate, dioxane and tetrahydrofuran. The solvent composition was fixed so as to elute all of the components of the sample mixture in a practical period of 2 h. Satisfactory separation of the ten components was obtained with the n-hexane-ethanol (90:10) system. The presence of methanol as a modifier in the n-hexane was effective in reducing the elution time, but the separation was not as satisfactory. Chloroform or dioxane was useful only for the separation of Ser, Asn and Gln. Acetone, methyl ethyl ketone, ethyl acetate and tetrahydrofuran were not suitable for practical separations of Dns-amino acids.     

The Analysis of Air for Acetone Cyanohydrin Using Solid Sorbent Sampling and Gas Chromatography

Abstract

A method for sampling and analysis of airborne acetone cyanohydrin is described. The analyte is collected on Porapak QS, a silylated styrene-divinylbenzene porous polymer. Samples are desorbed with ethyl acetate and analyzed by gas chromatography using a nitrogen-specific detector and a teflon column packed with 5% OV-17 on Chromosorb T. The detection limit is estimated to be 0.1 μg/mL acetone cyanohydrin in ethyl acetate. The method was tested by evaporating from 1.0 to 50 μg of the analyte onto sorbent beds of Porapak QS and exposing the samples to a humidified airstream for 15 min. Quantitative recovery was obtained for samples stored for one day at ambient temperature or for seven days if the samples were refrigerated immediately after collection.     

Optimisation of programmable temperature vaporizer-based large volume injection for determination of pesticide residues in fruits and vegetables using gas chromatography-mass spectrometry

The applicability of programmable temperature vaporizer (PTV) solvent vent injection to the gas chromatographic (GC) determination of pesticide residues in fruits and vegetables was evaluated with the aim of miniaturizing the current multiresidue method. For that purpose 24 pesticides representing different chemical classes were initially chosen for optimisation of the large volume injection (LVI) parameters. Various parameters related to the optimum injector performance were tested for several types of packed and empty liners using both fast (at-once) and speed-controlled PTV solvent vent injection of standard solutions in ethyl acetate. In the next step, several packed and empty liners were evaluated for their suitability for pesticide multiresidue analysis. Parameters identified as optimal were then applied for PTV solvent vent injection of sample extracts prepared using the miniaturized multiresidue method to assess the long-term stability of the system. The combined use of large volume injection of 10 microl ethyl acetate extract into an empty multi-baffled or a CarboFrit packed liner using PTV injectors and GC-MS analysis enabled the detection and quantification of 124 pesticides in fruit and vegetable samples at the 0.01 mg/kg level using miniaturized reversed-phase solid-phase extraction (RP-SPE) of diluted acetone extract and clean-up on a small anion-exchange SPE column.     

Comparison of the efficiency of different GLC multi-residue methods on crops containing pesticide residues

Summary The efficiency of the extraction methods with acetone and with ethyl acetate are compared with regard to the multi-pesticide residue determination in fruits and vegetables. The ethyl acetate-method gave higher recoveries for polar pesticides and seems somewhat easier, quicker and cheaper in handling but some co-extractives in the GC-extract are observed. In general, both methods gave acceptable and equivalent recoveries for the pesticides tested.     

Selective pressurized liquid extraction of estrogenic compounds in soil and analysis by gas chromatography-mass spectrometry

A selective pressurized liquid extraction (SPLE) method, followed by gas chromatography–mass spectrometry (GC–MS), for the simultaneous extraction and clean-up of estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), estriol (E3) and bisphenol A (BPA) from soil samples is described. The on-line clean-up of soil by SPLE was achieved using different organic matter retainers, including silica, alumina and Florisil, the most effective being silica. Thus, different amounts of silica, in conjunction with different extraction solvents (acetone, ethyl acetate, isohexane and dichloromethane), either alone or in combination, were used to extract the target chemicals from spiked soil samples. It was shown that 3 g silica resulted in satisfactory rates of recovery of target compounds and acetone:dichloromethane (1:3, v/v) was efficient in extracting and eluting estrogenic compounds for SPLE. Variables affecting the SPLE efficiency, including temperature and pressure were studied; the optimum parameters were 60 °C and 1500 psi, respectively. The limits of detection (LODs) of the proposed method were 0.02–0.37 ng g⁻¹ for the different estrogenic chemicals studied. The outputs using the proposed method were linear over the range from 0.1 to 120 ng g⁻¹ for E1, E2, EE2, 0.2–120 ng g⁻¹ for E3, and 0.5–120 ng g⁻¹ for BPA. The optimized method was further verified by performing spiking experiments in natural soil matrices; good rates of recovery and reproducibility were achieved for all selected compounds and the method was successfully applied to soil samples from Northeast Scotland, for the determination of the target compounds.     

分散固相萃取/高效液相色谱-串联质谱法检测大葱中虫酰肼、涕灭威及其衍生物的农药残留

采用分散固相萃取法净化(DSPE),高效液相色谱-串联质谱法(HPLC-MS/MS)在分时段多反应监测模式下对大葱中的虫酰肼、涕灭威及其衍生物进行测定,外标法定量,并对比了乙酸乙酯和乙腈作为提取剂的提取效果.结果表明,采用乙腈为提取剂时,4种农药在10～120μg/L范围内线性关系良好,且方法的定量下限(LOQ)均低于...     

添加丙酮与乙酸乙酯对生物油稳定性的影响

为了探究丙酮与乙酸乙酯对生物油储存特性的影响,将不同质量分数（3%、6%、9%、12%、15%）的丙酮和乙酸乙酯分别加入到生物油中,考察各组生物油理化特性随储存时间的变化。结果表明,添加丙酮和乙酸乙酯降低了生物油的含水率,且乙酸乙酯对生物油水分的降低效果优于丙酮。储存35 d后,15%乙酸乙酯组生物油的含水率为13.41%,比空白组（16.32%）降低了17.8%。加入添加剂后各组生物油的运动黏度均显著下降,与乙酸乙酯相比,丙酮对运动黏度影响较大。随着添加剂添加比例的增加,生物油运动黏度降低。储存35 d后,添加丙酮质量分数为3%、6%、9%、12%、15%的实验组生物油的运动黏度比空白组分别降低了37.20%、57.78%、71.92%、79.79%、84.67%。两种添加剂均能使生物油的pH值略微增大。红外光谱分析和气相色谱质谱联用分析显示,丙酮和乙酸乙酯抑制了生物油的老化反应。