Optimization of microwave-assisted extraction of hydrocarbons in marine sediments: comparison with the Soxhlet extraction method

Microwave energy was applied to extract polycyclic aromatic hydrocarbons (PAHs) and linear aliphatic hydrocarbons (LAHs) from marine sediments. The influence of experimental conditions, such as different extracting solvents and mixtures, microwave power, irradiation time and number of samples extracted per run has been tested using real marine sediment samples; volume of the solvent, sample quantity and matrix effects were also evaluated. The yield of extracted compounds obtained by microwave irradiation was compared with that obtained using the traditional Soxhlet extraction. The best results were achieved with a mixture of acetone and hexane (1:1), and recoveries ranged from 92 to 106%. The extraction time is dependent on the irradiation power and the number of samples extracted per run, so when the irradiation power was set to 500 W, the extraction times varied from 6 min for 1 sample to 18 min for 8 samples. Analytical determinations were carried out by high-performance liquid chromatography (HPLC) with an ultraviolet-visible photodiode-array detector for PAHs and gas chromatography (GC) using a FID detector for LAHs. To test the accuracy of the microwave-assisted extraction (MAE) technique, optimized methodology was applied to the analysis of standard reference material (SRM 1941), obtaining acceptable results.     

Microwave assisted extraction of polycyclic aromatic hydrocarbons from atmospheric particulate samples

For several years, microwave assisted extraction (MAE) was applied to extract organic compounds such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, etc., from soils, sediments and standard reference materials. Very few authors applied this methodology for the extraction of PAHs from atmospheric particulate matter. In the present study, MAE of polycyclic aromatic hydrocarbons with hexane/acetone (1:1) from real atmospheric particulate samples was investigated and the effect of microwave energy and irradiation time studied. The yields of extracted compounds obtained by microwave irradiation were compared with those obtained using traditional Soxhlet extraction. MAE was evaluated using spiked real atmospheric particulate samples and two standard reference materials. Analytical determinations of PAHs were carried out by high performance liquid chromatography (HPLC) with ultraviolet and fluorescence detection. The best recoveries were achieved with a microwave energy of 400 W and an irradiation time of 20 min.     

Novel approach to microwave-assisted extraction and micro-solid-phase extraction from soil using graphite fibers as sorbent

A single-step extraction-cleanup procedure involving microwave-assisted extraction (MAE) and micro-solid-phase extraction (micro-SPE) has been developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) from soil samples. Micro-SPE is a relatively new extraction procedure that makes use of a sorbent enclosed within a sealed polypropylene membrane envelope. In the present work, for the first time, graphite fiber was used as a sorbent material for extraction. MAE-micro-SPE was used to cleanup sediment samples and to extract and preconcentrate five PAHs in sediment samples prepared as slurries with addition of water. The best extraction conditions comprised of microwave heating at 50 degrees C for a duration of 20 min, and an elution (desorption) time of 5 min using acetonitrile with sonication. Using gas chromatography (GC)-flame ionization detection (FID), the limits of detection (LODs) of the PAHs ranged between 2.2 and 3.6 ng/g. With GC-mass spectrometry (MS), LODs were between 0.0017 and 0.0057 ng/g. The linear ranges were between 0.1 and 50 or 100 microg/g for GC-FID analysis, and 1 and 500 or 1000 ng/g for GC-MS analysis. Granular activated carbon was also used for the micro-SPE device but was found to be not as efficient in the PAH extraction. The MAE-micro-SPE method was successfully used for the extraction of PAHs in river and marine sediments, demonstrating its applicability to real environmental solid matrixes.     

Microwave-assisted extraction method for the determination of atrazine and four organophosphorus pesticides in oranges by gas chromatography (GC)

A simple and rapid microwave assisted extraction (MAE) method is presented for the determination of atrazine and four organophosphorus pesticides (parathion-methyl, chlorpyriphos, fenamiphos and methidathion) in orange peel. The experimental variables that affect the MAE method, such as temperature, sample quantity, extraction time, nature and volume of organic solvents, were optimized. The MAE method was optimized using an experimental design. The results suggest that temperature and sample quantity are statistically significant factors. It was concluded that the five pesticides could be efficiently extracted from 1.5–2.5 g of orange peel with 10 mL of hexane/acetone (1?:?1) mixture at 90?°C in 9 min with microwave power set at 50% (475 W). After optimization these factors, recoveries ranged from 93 to 101% with a relative standard deviation ranging from 1 to 3%. The extracts were analyzed by gas chromatography with a nitrogen-phosphorus detector (GC-NPD).     

Determination of polycyclic aromatic hydrocarbons in marine sediments by high-performance liquid chromatography after microwave-assisted extraction with micellar media

A simple and rapid method is developed for extraction and determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. The procedure was based on the microwave-assisted extraction of PAHs in marine sediment samples using a micellar medium of Polyoxyethylene 10 lauryl ether as extractant. Two-level factorial designs have been used to optimize the microwave extraction process. The analysis of extracts has been carried out by HPLC with UV detection. Fortified sediments gave an average recovery between 85.70 and 100.73%, with a relative standard deviation of 1.77-7.0% for PAHs with a ring number higher than three.     

Determination of polycyclic aromatic hydrocarbons in aqueous samples by microwave assisted headspace solid-phase microextraction and gas chromatography/flame ionization detection

The novel pretreatment technique, microwave-assisted heating coupled to headspace solid-phase microextraction (MA-HS-SPME) has been studied for one-step in situ sample preparation for polycyclic aromatic hydrocarbons (PAHs) in aqueous samples before gas chromatography/flame ionization detection (GC/FID). The PAHs evaporated into headspace with the water by microwave irradiation, and absorbed directly on a SPME fiber in the headspace. After being desorbed from the SPME fiber in the GC injection port, PAHs were analyzed by GC/FID. Parameters affecting extraction efficiency, such as SPME fiber coating, adsorption temperature, microwave power and irradiation time, and desorption conditions were investigated.Experimental results indicated that extraction of 20 mL aqueous sample containing PAHs at optional pH, by microwave irradiation with effective power 145 W for 30 min (the same as the extraction time), and collection with a 65 μm PDMS/DVB fiber at 20 °C circular cooling water to control sampling temperature, resulted in the best extraction efficiency. Optimum desorption of PAHs from the SPME fiber in the GC hot injection port was achieved at 290 °C for 5 min. The method was developed using spiked water sample such as field water with a range of 0.1-200 μg/L PAHs. Detection limits varied from 0.03 to 1.0 μg/L for different PAHs based on S/N = 3 and the relative standard deviations for repeatability were <13%. A real sample was collected from the scrubber water of an incineration system. PAHs of two to three rings were measured with concentrations varied from 0.35 to 7.53 μg/L. Recovery was more than 88% and R.S.D. was less than 17%. The proposed method is a simple, rapid, and organic solvent-free procedure for determination of PAHs in wastewater.     

Improved ultrasonic extraction procedure for the determination of polycyclic aromatic hydrocarbons in sediments

The aim of this work was to optimize an ultrasonic extraction procedure for the determination of polycyclic aromatic hydrocarbons (PAHs) in sediments and to compare it with the reflux procedure using methanolic potassium hydroxide. Sample extracts were purified with a miniaturized silica gel chromatographic column and analyzed by gas chromatography-mass spectrometry (GC-MS). Ultrasonication using n-hexane-acetone (1:1, v/v) solvent mixture on dried homogenized marine sediment gave better precision (smaller relative standard deviation (RSD) values) and comparable quantities of individual PAH's compared to the reflux procedure. Ultrasonication with the n-hexane-acetone (1:1, v/v) mixture, utilizing four 15 min extraction cycles, was found to be sufficient for extracting PAHs from wet sediments. The optimized ultrasonic extraction procedure extracted aliphatic and aromatic hydrocarbons from the National Institute of Standards and Technology SRM 1941a with recoveries greater than 90%. The major advantages of ultrasonication compared to the reflux method are the lower extraction times, simplicity of the apparatus and extraction procedure. The optimized ultrasonication procedure has been used in our laboratory to extract hydrocarbons from naturally wet sediments from rivers, and coastal and marine areas.     

Monitoring of PAHs in air by collection on XAD-2 adsorbent then microwave-assisted thermal desorption coupled with headspace solid-phase microextraction and gas chromatography with mass spectrometric detection

Microwave-assisted thermal desorption (MAD) coupled to headspace solid-phase microextraction (HS-SPME) has been studied for in-situ, one-step, sample preparation for PAHs collected on XAD-2 adsorbent, before gas chromatography with mass spectrometric detection. The PAHs on XAD-2 were desorbed into the extraction solution, evaporated into the headspace by use of microwave irradiation, and absorbed directly on a solid-phase microextraction fiber in the headspace. After desorption from the SPME fiber in the hot GC injection port, PAHs were analyzed by GC–MS. Conditions affecting extraction efficiency, for example extraction solution, addition of salt, stirring speed, SPME fiber coating, sampling temperature, microwave power and irradiation time, and desorption conditions were investigated. Experimental results indicated that extraction of 275 mg XAD-2, containing 10–200 ng PAHs, with 10-mL ethylene glycol–1 mol L⁻¹ NaCl solution, 7:3, by irradiation with 120 W for 40 min (the same as the extraction time), and collection with a PDMS–DVB fiber at 35 °C, resulted in the best extraction efficiency. Recovery was more than 80% and RSD was less than 14%. Optimum desorption was achieved by heating at 290 °C for 5 min. Detection limits varied from 0.02 to 1.0 ng for different PAHs. A real sample was obtained by using XAD-2 to collect smoke from indoor burning of joss sticks. The amounts of PAHs measured varied from 0.795 to 2.53 ng. The method is a simple and rapid procedure for determination of PAHs on XAD-2 absorbent, and is free from toxic organic solvents.     

Screening and confirmation of PAHs in vegetable oil samples by use of supercritical fluid extraction in conjunction with liquid chromatography and fluorimetric detection

A fast, simple, non-destructive method for the direct screening of polycyclic aromatic hydrocarbons (PAHs) in vegetable oil samples is proposed. The method uses a supercritical fluid extraction (SFE) system coupled on-line with a fluorimetric detector to determine PAHs. This special assembly avoids the main problems encountered in the determination of PAHs in complex matrices such as vegetable oils. PAHs are selectively extracted by using silica gel in the thimble and cleaned up by passage through a C18 column. Interferences are preferentially retained by the silica gel during the SFE process while PAHs are adsorbed in the C18 column and the remainder of the matrix is sent to waste. Finally, the C18 column is purged to remove residual CO₂ gas and adsorbed PAHs are recovered by desorption with a solvent. The extracts from positive samples are subsequently analyzed by liquid chromatography (LC) with fluorescence detection. The proposed method allows the confirmation of vegetable oil safety and hence provides a new tool for consumer protection.     

Solid-phase extraction clean-up procedure for the analysis of PAHs in lichens

A clean-up procedure based on a solid-phase extraction column was optimized for determination of polycyclic aromatic hydrocarbons (PAHs) in lichen extracts to remove co-extracted compounds from the matrix in the final extract. Several kinds of solid phases were evaluated: normal phase (-NH₂ and alumina), strong anion exchange and reversed phase. The -NH₂ columns were the most effective by using a packed solid bed of 500?mg. The lichen raw extract was loaded on the column previously conditioned with dichloromethane and hexane. Hexane (0.5?mL) was used as rinsing solvent, and PAHs were quantitatively eluted (80–97%) using 2?mL of hexane–dichloromethane (65–35) as eluting solvent. In these conditions, even the heaviest PAHs were quantitatively eluted. The optimized SPE method provides a short time and low-solvent-consumption sample clean-up compared with other conventional methods based on column chromatography. The analytical procedure, dynamic sonication-assisted extraction, followed by the optimized solid-phase extraction clean-up, was used to determine the 16 EPA priority PAHs from native lichens collected from the Aragon valley in central Pyrenees. The PAH concentrations in lichen samples ranged from 352 to 1654?ng?g^?1, and the minimum concentration value was established as the regional reference PAH levels in the area.     

Comparison of microwave-assisted extraction of aloe-emodin in aloe with Soxhlet extraction and ultrasound-assisted extraction

This paper reports the extraction of aloe-emodin from aloe by microwave-assisted extraction.The effects of various factors,including the solvent,the ratio (mL/g) of the solvent to the sample,microwave irradiation time and microwave power,were discussed in the experiments.The yield of aloe-emodin was determined by HPLC.The optimized conditions for microwave-assisted extraction of aloe-emodin were concluded as follows: the solvent is 80% ethanol (V/V) solution,microwave irradiation time is 3 min and microwave...     

Simultaneous microwave-assisted extraction of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, phthalate esters and nonylphenols in sediments

A new method was developed for the simultaneous extraction of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate esters (PEs), nonylphenols (NPs) and nonylphenol mono- and diethoxylates (NP1EOs and NP2EOs, respectively) in sediment samples by means of a closed microwave system. The extractions were carried out at 21 psi and 80% of microwave power and 15 ml of acetone were used as the common extraction solvent. The filtered extract was further fractionated in two groups using Florisil cartridges: PAHs and PCBs were eluted with n-hexane:toluene (4:1) and the PEs, NPs and ethoxylates were eluted with ethyl acetate. All the compounds were analysed by gas chromatography-mass spectrometry (GC-MS). In case of PAHs and PCBs, the developed method was validated by comparison of the results obtained for the certified reference material NIST 1944 with the certified values. In the absence of a reference material for phthalate esters and nonylphenols, one sediment sample was extracted twice under the optimal conditions in order to check than an exhaustive extraction of the analytes occurred. This method is currently used in the study of the distribution of those organic contaminants in the estuaries of the Bay of Biscay (Spain).     

快速溶剂萃取-气相色谱-串联质谱法分析海洋沉积物中16种多环芳烃

建立了快速溶剂萃取（ASE）-气相色谱-串联质谱（GC-MS/MS）分析海洋沉积物中16种多环芳烃（PAHs）的分析方法。样品由正己烷-丙酮（1∶1,v/v）溶液萃取,经无水硫酸钠脱水、氮吹浓缩后,采用硅胶固相萃取小柱进行净化,然后经HP-5MS色谱柱（30 m×0.25 mm×0.25 μm）分离,在电子轰击电离源下以多反应监测（MRM）模式进行检测,内标法定量。分析结果表明,16种PAHs在0.01~1.00 mg/L范围内线性关系良好,相关系数（R）大于0.997;目标物的加标回收率为75.8%~97.8%;日内与日间精密度（RSD）均小于10%。当取样量为20.0 g时,16种PAHs的方法检出限为0.048~0.234 μg/kg。该法快速、准确、稳定,能够满足海洋沉积物中痕量PAHs的测定。     

Dispersive solid-phase extraction clean up combined with Soxhlet extraction for the determination of 16 PAHs in soil samples by GC-MS

Dichloromethane soil samples extracts were prepared using Soxhlet extraction technique, and after clean-up step, gas chromatography-mass spectrometry analysis of 16 priority polycyclic aromatic hydrocarbons (PAHs) was carried out. A comparison of dispersive solid-phase extraction (dSPE) and column chromatography (cC), as clean-up techniques, was evaluated. Six different sorbents (silica, diatomaceous earth, primary–secondary amine, C18, clinoptilolite and florisil) were tested as dispersive clean-up sorbents versus activated silica and alumina for cC. Best results for three concentration levels among dSPE were obtained using diatomaceous earth, with recovery values in the range of 75–112% for 13 of 16 analysed compounds, while cC recoveries were in the range of 75–111% for all analysed PAHs. Analysis of 12 soil samples from urban area of Ni? (Serbia) singled out acenaphthene as the most abundant compound.     

超声-微波协同萃取装置用于土壤中多环芳烃的分析

本研究将开放式微波和直接超声波振荡两种不同的能量方式相结合,研制出超声-微波协同萃取装置。通过萃取土壤中微量多环芳烃(PAHs),对方法和仪器的可行性进行了初步评价。结果表明,在60 mL二氯甲烷-正已烷(1∶1,V/V)的混合萃取剂,100 W微波辐射功率(超声振动功率固定为50 W),萃取9~10m in,土壤中多环芳烃回收率达86.6%,相对标准偏差约4.0%。与索氏抽提、高压密闭和开放式微波等萃取方法相比,本方法具有样品容量大,萃取时间短,萃取效率受样品中含水量和溶剂极性影响小等优点。     

A new and fast extraction method for the determination of priority phenols from marine sediments by liquid chromatography

A new and fast method for the determination of priority phenols in marine sediment samples by high-performance liquid chromatography using microwave-assisted micellar extraction is optimized. This study is carried out using the nonionic surfactants polyoxyethylene 9 lauryl ether (polidocanol) and genapol X-080 as extractants. Parameters studied include surfactant concentration, solution pH, extraction time, and power. Once the method is optimized, it is applied to different spiked marine sediments from of the Canary Islands coastlines (Spain). The results obtained indicate that a power irradiation of 500 W for 2 min achieved the best extraction efficiency (approximately 100% recovery) and less than 10% relative standard deviation. Detection limits are obtained in the 2-20 microg/g range for the phenols studied. Finally, the proposed method provides a simple, fast, and organic solvent-free procedure to analyze phenols from marine sediment samples.     

Multivariate optimization of a liquid-liquid extraction of the EPA-PAHs from natural contaminated waters prior to determination by liquid chromatography with fluorescence detection

This paper reports the multivariate optimization of a liquid–liquid extraction procedure for the determination of 15 EPA-polycyclic aromatic hydrocarbons (PAHs) by high-performance liquid chromatography with fluorescence detection. A Doehlert design was used to find optimum conditions for the procedure through Response Surface Methodology. Three variables (total volume of hexane, number of extraction steps and duration of such steps) were elected as factors in the optimization study. A principal component analysis (PCA) was run with optimized data, resulting in four groups of PAHs, ordered according to their molecular weight. Final working conditions were established in order to achieve a more robust methodology in relation to all fifteen PAHs under study. Best results could be observed when 77 mL of hexane were divided in four consecutive extraction steps with 18 min each. These experimental conditions were applied in the analysis of a spiked river water sample, and the recoveries varied between 80.9 and 106%, with an average value of 97.1 ± 6.8%. The application of the methodology to river water showed that the method has a good average precision for the studied PAHs.     

Optimization by factorial design of focused microwave assisted extraction of polycyclic aromatic hydrocarbons from marine sediment

The Focused Microwave (FMW) assisted extraction for organic contaminant analysis, such as polycyclic aromatic hydrocarbons (PAHs), in environmental matrices, was studied and optimized using a factorial design. The effects and interactions of five parameters on the extraction recovery were investigated in a few experiments with a good accuracy: irradiation power and time, volume and nature of solvent, and percentage of moisture of the matrix. The results show that the percentage of water added to the freeze-dried matrix can significantly increase the extraction recovery. The irradiation power has also a positive effect. The choice of solvent is significant: a mixture of heptane/ethanol (80/20, v/v) allows better results than dichloromethane. Some interactions between percentage of moisture and the two previous parameters have been demonstrated: the effect of power and nature of solvent depends on the water content. Some optimal conditions have been established: 10 mL of heptane/ethanol (80/20, v/v), extraction time of 2 min, and different possible pairs of moisture content and irradiation power (140 W and 0% of moisture or 20 W and 40% of moisture) according to the need and wish of the experimentalist; or 10 mL of dichloromethane, extraction time of 2 min, 20 W and 40% of moisture. These optimized conditions provide very good recoveries compared to conventional extraction such as Soxhlet (near 100%) for the model matrix (a marine sediment) used for the factorial design. FMW extraction is a good alternative to Soxhlet extraction with reduction of time and reduction of solvent volume. This study shows that it is possible to substitute chlorinated solvent by a less toxic solvent, like a mixture of heptane and ethanol.     

Multi-determination of organic pollutants in water by gas chromatography coupled to triple quadrupole mass spectrometry

A multi-determination method has been developed for the determination and confirmation of 68 organic pollutants in water samples by gas chromatography coupled to triple quadrupole mass spectrometry (GC-MS/MS). The following chemical families were determined in a chromatographic run of less than 26?min: polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenylethers (PBDEs), and pesticides (organochlorine, organophosphorus, triazine and others). The sample preparation involved a liquid-liquid extraction (LLE) procedure, obtaining recoveries ranging from 70 to 130% when dichloromethane was used as the extracting solvent. The detection limits of the proposed method were between 0.75 and 19.8?ng?L^?1. Samples from the Maipo River in central Chile were taken from 29 different points. Seven pesticides and two PAHs were detected in field collected samples with concentrations ranging from 10 to 95?ngL^?1. Concentrations of benzo[a]pyrene in environmental samples ranged from 25 to 33?ngL^?1 and were near the maximum levels established by the European Union Directives (50?ng?L^?1).     

Optimised accelerated solvent extraction of PCBs and PAHs from compost

This study is the first thorough method optimisation for accelerated solvent extraction (ASE) of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) from chemically dried compost. For PCBs, optimised solvent composition, temperature, pressure, number of static cycles, duration, and flush volume were as follows: toluene/acetone 1?:?3 (v/v), 120°C, 2000?psi, 3?×?5?min, and 50%, respectively. Limits of quantification and method precision were between 0.16 and 2.46?µg?kg^?1 dw and 6–17% respectively for individual PCBs. Absolute recoveries of isotope-labelled extraction standards used for each of the analytes ranged from 65 to 105% and relative recoveries were between 85 and 99%. The method proofed to be robust and was successfully applied to different compost samples.

The optimisation of PAHs extraction was performed and resulted in the following conditions: solvent: hexane/acetone 1/3 (v:v), temperature: 140°C, pressure: 1500?psi, extraction time: 3?×?5?min, and 50% flush volume. Limits of detection and method precision for individual PAHs were between 1.1 and 37.2?µg?kg^?1?dw and 12–34% respectively. Absolute and relative recoveries ranged from 24 to 68% and from 85 to 99%, respectively. Optimal extraction conditions for PAHs were more difficult to determine due to the inhomogeneous distribution of PAHs in samples. However, the method appeared to be feasible and suggestions for further improvements are presented.