Evaluation of Soxhlet extraction, accelerated solvent extraction and microwave-assisted extraction for the determination of polychlorinated biphenyls and polybrominated diphenyl ethers in soil and fish samples

Three commonly applied extraction techniques for persistent organic chemicals, Soxhlet extraction (SE), accelerated solvent extraction (ASE) and microwave-assisted extraction (MAE), were applied on soil and fish samples in order to evaluate their performances. For both PCBs and PBDEs, the two more recent developed techniques (ASE and MAE) were in general capable of producing comparable extraction results as the classical SE, and even higher extraction recoveries were obtained for some PCB congeners with large octanol-water partitioning coefficients (K_ow). This relatively uniform extraction results from ASE and MAE indicated that elevated temperature and pressure are favorable to the efficient extraction of PCBs from the solid matrices. For PBDEs, difference between the results from MAE and ASE (or SE) suggests that the MAE extraction condition needs to be carefully optimized according to the characteristics of the matrix and analyte to avoid degradation of higher brominated BDE congeners and improve the extraction yields.     

Comparison of accelerated solvent extraction with microwave-assisted extraction and Soxhlet for the extraction of chlorinated biphenyls in soil samples

The extraction and determination of chlorinated biphenyls (CBs) in soils and solid wastes is an ongoing subject of study. This is an overview article that compares the microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) techniques. The extraction of CBs by ASE has been optimised taking into account the variation of pressure, temperature and extraction time by means of experimental design and the Simplex approach. The recoveries obtained under the optimum conditions are compared and discussed with those obtained from MAE and Soxhlet extractions.     

Extraction of polychlorinated biphenyls from soils by automated focused microwave-assisted Soxhlet extraction

The application of a new focused microwave-assisted Soxhlet extractor for the extraction of polychlorinated biphenyls from differently aged soils is here presented. The new extractor overcomes the disadvantages of previous devices based on the same principle and enables a fully automated extraction of two samples simultaneously. The variables affecting the extraction step (namely, power of irradiation, irradiation time, extractant volume, extractant composition and number of extraction cycles) have been optimized using experimental design methodology. The optimized method has also been applied to a certified reference material (CRM910-050 "real" contaminated soil) for quality assurance validation. Quantification of the target compounds has been performed by GC with ion-trap MS. The mass spectrometer was operated in the electron-ionization mode, with selected-ion monitoring at m/z 152, 186, 292, 326 and 498. The results obtained have demonstrated that this approach is as efficient as conventional Soxhlet but with a drastic reduction of both extraction time (70 min vs. 24 h for the "real" contaminated soil) and organic solvent disposal, as 75-80% of the extractant is recycled.     

Determination of 26 polychlorinated biphenyls congeners in soil samples using microwave-assisted extraction with open vessel and gas chromatography

A procedure focused on microwave-assisted extraction in open vessel (MAE-OV) and gas chromatography with electron capture detection (GC-ECD) was used for the determination of 26 congeners of polychlorinated biphenyls (PCBs) in soil samples. The limit of detection (LOD) and limit of quantification (LOQ) were evaluated for commercial PCBs mixture Aroclor1260. LOD and LOQ were calculated for each PCB congener, in the ranges (0.03–0.27?ng?g^?1) and (0.11–0.70?ng?g^?1), respectively. After optimization, 26 PCBs congeners were successfully extracted from soil samples with recovery amounts ranging between 84.7% and 117.3% for all PCBs congeners. The evaluated method of MAE-OV showed good separation and extraction of all PCBs congeners from soil samples. Extraction parameters such as solvent choice, power and extraction time were investigated. This study indicated that MAE-OV could be an interesting alternative method to extract PCBs from soils, since it is economical, easy, fast and requires low amounts of solvents.     

Optimization of a microwave-assisted extraction method for the analysis of polychlorinated biphenyls in ash samples

An alternative method for the extraction of polychlorinated biphenyls (PCBs) in ash samples, which is less time and solvent consuming than Soxhlet extraction, is presented. A study was carried out to evaluate the possibilities of microwave-assisted extraction (MAE) to determine exactly which parameters affect the efficiency of the process, since direct extrapolation of extraction conditions for PCBs in other solid matrices, failed when applied to coplanar congeners in ash samples. Influence of the organic solvent on the yield of the extraction was first evaluated using two ash samples with different percentages of carbon. Once the extraction solvent was fixed, the effects of solvent volume, extraction temperature and extraction time were investigated using an experimental design. It was found that the volume of organic solvent played a more important role in the extraction efficiency than the other factors. In the optimal conditions microwave extractions were performed at 110 degrees C. for 10 min and using 30 ml of toluene. Recoveries higher than 80% were obtained for all the highly chlorinated congeners. including coplanar species, in a spiked ash sample containing a relatively high concentration of carbon. The proposed method was also applied to the determination of PCBs in a reference material of urban dust. Recoveries were similar to those obtained for spiked ash samples.     

Comprehensive comparison of classic Soxhlet extraction with Soxtec extraction, ultrasonication extraction, supercritical fluid extraction, microwave assisted extraction and accelerated solvent extraction for the determination of polychlorinated biphenyls in soil

This paper compares the extraction effectiveness of six different commonly applied extraction techniques for the determination of PCBs in soil. The techniques included are Soxhlet, Soxtec, ultrasonication extraction, supercritical fluid extraction, microwave-assisted extraction and accelerated solvent extraction. For none of the techniques were the extraction conditions optimized, but instead the extraction parameters were based on the experience from previous successful investigation published by a number of research groups worldwide. In general, all extraction techniques were capable of producing accurate data for one native PCB contaminated soil diluted with another soil sample to obtain two concentration levels. It could therefore be concluded that any of the investigated techniques can be used with success if the extraction conditions applied are chosen wisely.     

Direct competitive ELISA for the determination of polychlorinated biphenyls in soil samples

A direct competitive ELISA for determination of polychlorinated biphenyls (PCB) in soil samples was described. The standard calibration curve based on Delor 103 (Aroclor 1242) was constructed in the dynamic range of 10-1000 micro g L(-1) and a detection limit of 5.0-12.9 micro g L(-1) (or 0.5-1.29 micro g g(-1) soil) was achieved. When spiked soil samples were extracted with methanol recoveries were 90.6-106.3 %. The effect of methanol and DMSO on assay signal and sensitivity was established. Eight PCB-contaminated soil samples were analyzed by ELISA and gas chromatography (GC). The ELISA results from Soxhlet extraction were in a good agreement with those of GC (correlation coefficient 0.9866; n=8). Except for one soil sample the results from ELISA with methanol extraction were not significantly different from those from GC.     

Optimisation of microwave-assisted extraction for the determination of nonylphenols and phthalate esters in sediment samples and comparison with pressurised solvent extraction

Microwave-assisted extraction (MAE) of nonylphenols (NP), nonylphenol mono- and diethoxylates (NP1EO and NP2EO, respectively) and phthalate esters was optimised using an experimental design approach. A D-optimal mixture design was used to optimise the pressure inside the extraction vessel (110-207 kPa), the extraction time (5-25 min) and the extraction solvent (methanol, acetone or n-hexane) or the solvent mixture for the microwave-assisted extraction. Percentage of microwave power (80%) and solvent volume (15 ml) were fixed in all the experiments. As a consequence, the optimum extraction of these compounds was carried out at an intermediate pressure (159 kPa) with pure methanol and during 15 min. Moreover, solid phase extraction was also optimised for the clean-up of the extracts and C-18, LiChrolut^® and Oasis^® cartridges were studied in order to obtain the best recoveries of the compounds of interest. The highest recoveries were obtained with LiChrolut^® cartridges after the elution with ethyl acetate. The cleaned extracts were analysed in a gas chromatograph with mass spectrometric detection and in a liquid chromatograph with diode array and fluorescence detection (HPLC-DAD-UV-FLD). The same sediment was also extracted twice in order to check that an exhaustive extraction of the analytes had occurred. Finally, the optimised extraction method was compared with pressurised solvent extraction (PSE), using an estuarine sediment sample.     

Optimization and comparison of MAE, ASE and Soxhlet extraction for the determination of HCH isomers in soil samples

The microwave-assisted extraction (MAE), accelerated solvent extraction (ASE) and Soxhlet extraction of two isomers of hexachlorocyclohexane, alpha-HCH and gamma-HCH, from a polluted landfill soil have been optimized following different experimental designs. In the case of microwave-assisted extraction, the following variables were considered: pressure, extraction time, microwave power, percentage of acetone in n-hexane mixture and solvent volume. When ASE extraction was studied the variables were pressure, temperature and extraction time. Finally, the percentage of acetone in n-hexane mixture and the extraction time were the only variables studied for Soxhlet extraction. The concentrations obtained by the three extraction techniques were, within their experimental uncertainties, in good agreement. This fact assures the possibility of using both ASE and MAE techniques in the routine determination of lindane in polluted soils and sediments.     

Optimization and comparison of MAE, ASE and Soxhlet extraction for the determination of HCH isomers in soil samples

The microwave-assisted extraction (MAE), accelerated solvent extraction (ASE) and Soxhlet extraction of two isomers of hexachlorocyclohexane, α-HCH and γ-HCH, from a polluted landfill soil have been optimized following different experimental designs. In the case of microwave-assisted extraction, the following variables were considered: pressure, extraction time, microwave power, percentage of acetone in n-hexane mixture and solvent volume. When ASE extraction was studied the variables were pressure, temperature and extraction time. Finally, the percentage of acetone in n-hexane mixture and the extraction time were the only variables studied for Soxhlet extraction. The concentrations obtained by the three extraction techniques were, within their experimental uncertainties, in good agreement. This fact assures the possibility of using both ASE and MAE techniques in the routine determination of lindane in polluted soils and sediments. Received: 28 January 2000 / Revised: 28 March 2000 / Accepted: 31 March 2000     

Evaluation of a microwave-assisted extraction technique for the determination of polychlorinated biphenyls and organochlorine pesticides in sediments.

A microwave-assisted extraction (MAE) technique for the determination of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in marine sediment samples has been investigated. The analytes were extracted under different treatment conditions, such as temperature, time and extraction solvent. They were quantified by an isotope-dilution method, and the observed concentrations and recovery yields obtained under different conditions were compared. The results of a comparison between this MAE and other extraction techniques, such as pressurized fluid extraction, saponification, sonication, and Soxhlet extraction, are also given in this report. The techniques gave comparable results with the values obtained by other extraction techniques and the certified values in the samples. However, the observed concentration values of mono- and dichlorinated biphenyls varied depending on the extraction temperature.     

Pressurized liquid extraction in determination of polychlorinated biphenyls and organochlorine pesticides in fish samples

Pressurized liquid extraction (PLE) is a relatively new technique applicable for the extraction of persistent organic pollutants from various matrices. The main advantages of this method are short time and low consumption of extraction solvent. The effects of various operational parameters (i.e. temperature of extraction, number of static cycles and extraction solvent mixtures) on the PLE efficiency were investigated in this study. Fish muscle tissue containing 3.2% (w/w) lipids and native polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and other related compounds was used for testing. Purification of crude extracts was carried out by gel permeation chromatography employing Bio-Beads S-X3. Identification and quantitation of target indicator PCBs and OCPs was performed by high-resolution gas chromatography (HRGC) with two parallel electron-capture detectors (ECDs). Results obtained by the optimized PLE procedure were compared with conventional Soxhlet extraction (the same extraction solvent mixtures hexane–dichloromethane (1:1 v/v) and hexane–acetone (4:1 v/v) were used). The recoveries obtained by PLE operated at 90–120 °C were either comparable to “classic” Soxhlet extraction (for higher-chlorinated PCB congeners and DDT group) or even better (for lower chlorinated analytes). The highest recoveries were obtained for three static 5 min extraction cycles.     

Evaluation of microwave-assisted extraction for the analysis of polychlorinated biphenyls and organochlorine pesticides in fish

The efficiency of microwave-assisted extraction (MAE) was evaluated for the analysis of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in fish. An isotope dilution method was used for quantification via analysis of the samples by gas chromatography and mass spectrometry. MAE solvent, temperature, and time were optimized, and observed concentrations were compared. The MAE results were also compared to those of other extraction techniques (Soxhlet extraction, pressurized liquid extraction, saponification, and homogenization). Concentrations of PCBs and OCPs obtained by MAE at 120 degrees C for 10 min were comparable to those by the other techniques. The results suggest that MAE can be used for the analysis of PCBs and OCPs in fish.     

Simultaneous extraction of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and coplanar polychlorinated biphenyls from contaminated soil using pressurized liquid extraction

Pressurized liquid extraction (PLE) was studied for simultaneous extractions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), and of coplanar polychlorinated biphenyls (Co-PCBs) from a tightly bounded condition in the soil matrix. Temperatures were maintained at 175 and 200 degrees C, respectively, and two or three static cycles for single PLE with toluene and acetone/n-hexane were studied using a certified reference material to compare the effects of those conditions on recoveries. A single PLE with two static cycles at 150 degrees C and the repeated single PLE (additional PLE) were reference methods. Satisfactory recoveries were not obtained using tested single PLE (2,3,7,8-substituted PCDD/PCDFs and Co-PCBs average, average (avg.) 79-103%), but they were achieved using additional PLE (acetone/n-hexane, avg. 115-128%; toluene, avg. 111-132%). In addition, these methods and additional PLE of the reference method using acetone/n-hexane were not markedly different (avg. 123-128%). That fact suggests that the use of mixed solvents and additional PLE were more important factors than temperatures and static cycles of single PLE for quantitative and simultaneous extractions of those compounds from the soil.     

Analysis of polychlorinated biphenyls in aqueous samples by microwave-assisted headspace solid-phase microextraction

The hyphenated technique namely microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) was developed and studied for the simultaneous extraction/enrichment of polychlorinated biphenyls (PCBs) in aqueous samples prior to the quantification by gas chromatography (GC). The PCBs in aqueous media are extracted onto a solid-phase micro fibre via the headspace with the aid of microwave irradiation. The optimum conditions for obtaining extraction efficiency, such as the extraction time, addition of salts, addition of methanol, ratio of sample to headspace volume, and the desorption parameters were investigated. Experimental results indicated that the proposed MA-HS-SPME method attained the best extraction efficiency under the optimized conditions, i.e., irradiation of extraction solution (20 ml aqueous sample in 40 ml headspace vial with no additions of salt and methanol) under 30 W microwave power for 15 cycles (1 min power on and 3 min power off of each cycle). Desorption at 270 degrees C for 3 min provided the best detection results. The detection limit obtained were between 0.27 and 1.34 ng/l. The correlation coefficient for the linear dynamic range from 1 to 80 ng/l exceeded 0.99 for 18 PCBs.     

微波萃取/气相色谱-质谱测定土壤中的多氯联苯

分别对多氯联苯的微波萃取条件进行了优化。优化后的分析条件为微波功率1200 W,萃取温度115℃,萃取时间20 min,萃取溶剂为V(正己烷)∶V(丙酮)=1∶1。方法的检出限为20~30 ng/g,线性范围40~4000 ng/mL(多氯联苯总量),相关系数均大于0.9990,样品基体加标回收率为92.2%~115%,相对标准偏差为9.4%(n=6)。     

Determination of polychlorinated biphenyls in biota samples using simultaneous pressurized liquid extraction and purification

In order to reduce time and cost of analysis, a new pressurised liquid extraction method that automatically and rapidly achieves quantitative and selective (i.e., lipid-free) extraction of polychlorinated biphenyls (PCBs) in biota tissues was optimized. It consists of on-line clean-up by inclusion of sorbents in the extraction cell. The freeze-dried sample is dispersed with Florisil and loaded in the extraction cell containing an extra amount of Florisil. The extraction is performed under mild conditions using 55 ml of a dichloromethane-pentane (15:85) mixture, a temperature of 40 degrees C, a static extraction time of 10 min and two extraction cycles. The Florisil retains coextracted lipids from the matrix, and the extract, after pre-concentration, is clean enough for direct injection into GC-MS and GC-electron-capture detection (ECD). Quantitative recoveries (from 90 to 106%) are obtained for both native and spiked PCB congeners in samples with a high lipidic content (up to 42% dry mass, in spoonbill eggs). The reproducibility of replicate extractions was better than 11% relative standard deviation. Method detection limits were in the ranges of 0.001-0.004 and 0.002-0.07 ng g(-1) dry mass for GC-ECD and GC-MS-MS, respectively. The method was validated using the standard reference material SRM 2974 (a mussel tissue) from the US National Institute of Standards and Technology, compared to Soxhlet and matrix solid-phase dispersion extraction methods, and used to evaluate the contamination by PCBs in bivalves from South of Spain.     

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.     

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.