超临界流体萃取对大气飘尘中有机污染物的分析

采用超临界流体萃取与气相色谱／质谱联用技术对兰州市大气飘尘中有机污染物进行了测定。实验考察了对强致癌性化合物多环芳烃类萃取的最佳条件,在２６．０ＭＰａ,８０℃下,０．５ｍＬ甲醇做改性剂,用ＣＯ２作为超临界萃取介质,静态萃取１０ｍｉｎ后再以０．５ｍＬ／ｍｉｎ的流速动态萃取３０ｍｉｎ,对实际样品进行了定性定量分析,共检测出６９种有机污染物,该方法简便,快速,适合于飘尘中有机污染物的测定。     

Determination of polycyclic aromatic hydrocarbons in marine sediments using a new ASE-SFE extraction technique

In order to determine PAHs in marine sediment samples by GC/MS(SIM) a new extraction approach of ASE-SFE was evaluated using combined accelerated solvent extraction (ASE, dynamic and static mode) and supercritical fluid extraction (SFE, dynamic mode) without further purification of the sample. The solvents used for ASE-SFE were methylene chloride and carbon dioxide. The recovery data, precision and accuracy of the whole method were evaluated statistically. The average recoveries of PAHs, based on deuterated internal standards were 77% for 2-3-ring PAHs, 85% for 4-ring PAHs, 88% for 5-ring PAHs and 97% for 6-ring PAHs. The extraction time required for the ASE-SFE technique was 30 min, which is longer than in the case of independent use of ASE and shorter compared to SFE. ASE-SFE recoveries of PAHs from SRM marine sediment are comparable for (2-3-ring, 4-ring PAHs) or higher (5-ring, 6-ring PAHs) than reported for the conventional extraction methods of ASE and SFE. Method detection limits of (MDL) were statistically estimated. MDL values obtained for 15 PAHs compounds vary between 0.06 ngg(-1) and 3.54 ngg(-1).     

Supercritical fluid clean-up of environmental samples for the analysis of polycyclic aromatic hydrocarbons using time-of-flight secondary ion mass spectrometry.

A novel sample-pretreatment method for time-of-flight secondary ion mass spectrometry (TOF-SIMS) was developed using supercritical fluid extraction (SFE). In SFE, the extraction efficiency of a certain organic matter is controlled by the pressure and temperature of supercritical CO2. Two-step SFE (1st step at 10 Mpa, 40 degrees C; 2nd step at 30 MPa, 120 degrees C) was applied to diesel exhaust particles containing many kinds of n-alkanes and aromatic species. n-Alkanes and polycyclic aromatic hydrocarbons (PAHs) were extracted in the 1st and 2nd steps, respectively. This selectivity was utilized for the sample preparation of TOF-SIMS analysis. Diesel exhaust particles after the 1st step of extraction were analyzed with TOF-SIMS, aiming at PAHs as analytical targets. The obtained spectrum was simplified, and mass peaks of individual PAHs were easily assigned, because unwanted compounds, like n-alkanes, were selectively removed by SFE. Furthermore, a simple calculation elucidated the outline of the spectrum.     

Determination of polycyclic aromatic hydrocarbons in marine sediments using a new ASE-SFE extraction technique

In order to determine PAHs in marine sediment samples by GC/MS(SIM) a new extraction approach of ASE-SFE was evaluated using combined accelerated solvent extraction (ASE, dynamic and static mode) and supercritical fluid extraction (SFE, dynamic mode) without further purification of the sample. The solvents used for ASE-SFE were methylene chloride and carbon dioxide. The recovery data, precision and accuracy of the whole method were evaluated statistically. The average recoveries of PAHs, based on deuterated internal standards were 77% for 2–3-ring PAHs, 85% for 4-ring PAHs, 88% for ¶5-ring PAHs and 97% for 6-ring PAHs. The extraction time required for the ASE-SFE technique was 30 min, which is longer than in the case of independent use of ASE and shorter compared to SFE. ASE-SFE recoveries of PAHs from SRM marine sediment are comparable for (2–3-ring, 4-ring PAHs) or higher (5-ring, 6-ring PAHs) than reported for the conventional extraction methods of ASE and SFE. Method detection limits of (MDL) were statistically estimated. MDL values obtained for 15 PAHs compounds vary between 0.06 ngg^?1 and 3.54 ngg^?1.     

Optimisation of supercritical fluid extraction of polynuclear aromatic hydrocarbons from spiked soil and marine sediment standard reference material

 For the determination of 16 PAHs in soils and sediment samples by GC/FID and GC/MS, the dynamic off-line supercritical fluid extraction with both pure and modified carbon dioxide has been evaluated. The optimisation of extraction parameters was performed for four individual groups of PAHs according to their number of aromatic rings (2–3 rings, 4 rings, 5 rings and 6 rings) by varying pressure (200–510 bar), temperature (50–150 °C), extraction fluid volume (10–50 ml), and the methanol modifier concentration (0–10%). Using a five level spherical factorial experimental design the number of experiments required for optimisation was 45. In spiked soil samples extraction efficiencies of 80–100% were achieved for the individual groups of PAHs. At the optimal set of conditions 10–30% lower recoveries of PAHs were obtained for the standard reference material NIST SRM 1941a (marine sediment). The largest differences between extraction recoveries of native and spiked PAHs occurred at high molecular weight PAHs. Using SFE efficiency data for the standard reference material, cluster analysis proved that dividing the 16 PAHs into four groups according to their number of aromatic rings was appropriate and correct. Received: 2 February 1996/Revised: 26 November 1996/Accepted: 30 November 1996     

Ultrasonic/Soxhlet/supercritical fluid extraction kinetics of pyrethrins from flowers and allethrin from paper strips

Three different extraction methods (ultrasonic extraction (USE), Soxhlet extraction (SOX) and supercritical fluid extraction (SFE)) were compared for the extraction of pyrethrins from chrysanthemic flowers and commercial insecticide powder. Allethrin was extracted from paper strips. All extracts and the kinetics were analyzed by supercritical fluid chromatography and flame ionization detector. Received: 18 January 1999 / Revised: 29 June 1999 / /Accepted: 30 June 1999     

Ultrasonic/Soxhlet/supercritical fluid extraction kinetics of pyrethrins from flowers and allethrin from paper strips

Three different extraction methods (ultrasonic extraction (USE), Soxhlet extraction (SOX) and supercritical fluid extraction (SFE)) were compared for the extraction of pyrethrins from chrysanthemic flowers and commercial insecticide powder. Allethrin was extracted from paper strips. All extracts and the kinetics were analyzed by supercritical fluid chromatography and flame ionization detector. Received: 18 January 1999 / Revised: 29 June 1999 / /Accepted: 30 June 1999     

Effect of supercritical fluid extraction parameters and clay properties on the efficiency of phenanthrene extraction

Clay soils have specific properties that cause difficulty in the assessment and remediation of contaminated sites. Furthermore, polyaromatic hydrocarbons, when present in soil, are difficult to extract due to their nonpolar, high molecular weight characterization. In this study, the supercritical fluid (carbon dioxide) extraction (SFE) technique, with and without methanol modifier, was used for removal of PAHs (phenanthrene) from kaolinite, illite, and montmorillonite soils. The impact of SFE parameters (fluid pressure, fluid temperature, and time), and of clay properties (such as clay minerals content, initial moisture content, soil porosity or equivalent pores size, clay surface area, cation-exchange capacity, and clay-swelling index) on the removal efficiency of PAHs from clayey soils were investigated. The results of this investigation were used to develop a semi-empirical correlation between the recovery (i.e. the extraction efficiency) at any time and above mentioned parameters and properties.     

Highly sensitive determination of polycyclic aromatic hydrocarbons in ambient air dust by gas chromatography-mass spectrometry after molecularly imprinted polymer extraction

A method based on solid--phase extraction with a molecularly imprinted polymer (MIP) has been developed to determine five probable human carcinogenic polycyclic aromatic hydrocarbons (PAHs) in ambient air dust by gas chromatography-mass spectrometry (GC-MS). Molecularly imprinted poly(vinylpyridine-co-ethylene glycol dimethacrylate) was chosen as solid-phase extraction (SPE) material for PAHs. The conditions affecting extraction efficiency, for example surface properties, concentration of PAHs, and equilibration times were evaluated and optimized. Under optimum conditions, pre-concentration factors for MIP-SPE ranged between 80 and 93 for 10 mL ambient air dust leachate. PAHs recoveries from MIP-SPE after extraction from air dust were between 85% and 97% and calibration graphs of the PAHs showed a good linearity between 10 and 1000 ng L⁻¹ (r = 0.99). The extraction efficiency of MIP for PAHs was compared with that of commercially available SPE materials—powdered activated carbon (PAC) and polystyrene-divinylbenzene resin (XAD)—and it was shown that the extraction capacity of the MIP was better than that of the other two SPE materials. Organic matter in air dust had no effect on MIP extraction, which produced a clean extract for GC-MS analysis. The detection limit of the method proposed in this article is 0.15 ng L⁻¹ for benzo[a]pyrene, which is a marker molecule of air pollution. The method has been applied to the determination of probable carcinogenic PAHs in air dust of industrial zones and satisfactory results were obtained.     

Comparisons of soxhlet extraction, pressurized liquid extraction, supercritical fluid extraction and subcritical water extraction for environmental solids: recovery, selectivity and effects on sample matrix

Extractions of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil from a former manufactured gas plant site were performed with a Soxhlet apparatus (18 h), by pressurized liquid extraction (PLE) (50 min at 100 degrees C), supercritical fluid extraction (SFE) (1 h at 150 degrees C with pure CO2), and subcritical water (1 h at 250 degrees C, or 30 min at 300 degrees C). Although minor differences in recoveries for some PAHs resulted from the different methods, quantitative agreement between all of the methods was generally good. However, the extract quality differed greatly. The organic solvent extracts (Soxhlet and PLE) were much darker, while the extracts from subcritical water (collected in toluene) were orange, and the extracts from SFE (collected in CH2Cl2) were light yellow. The organic solvent extracts also yielded more artifact peaks in the gas chromatography (GC)-mass spectrometry and GC-flame ionization detection chromatograms, especially compared to supercritical CO2. Based on elemental analysis (carbon and nitrogen) of the soil residues after each extraction, subcritical water, PLE, and Soxhlet extraction had poor selectivity for PAHs versus bulk soil organic matter (approximately 1/4 to 1/3 of the bulk soil organic matter was extracted along with the PAHs), while SFE with pure CO2 removed only 8% of the bulk organic matrix. Selectivities for different compound classes also vary with extraction method. Extraction of urban air particulate matter with organic solvents yields very high concentrations of n- and branched alkanes (approximately C18 to C30) from diesel exhaust as well as lower levels of PAHs, and no selectivity between the bulk alkanes and PAHs is obtained during organic solvent extraction. Some moderate selectivity with supercritical CO2 can be achieved by first extracting the bulk alkanes at mild conditions, followed by stronger conditions to extract the remaining PAHs, i.e., the least polar organics are the easiest organics to extract with pure CO2. In direct contrast, subcritical water prefers the more polar analytes, i.e., PAHs were efficiently extracted from urban air particulates at 250 degrees C, with little or no extraction of the alkanes. Finally, recent work has demonstrated that many pollutant molecules become "sequestered" as they age for decades in the environment (i.e., more tightly bound to soil particles and less available to organisms or transport). Therefore, it may be more important for an extraction method to only recover pollutant molecules that are environmentally-relevant, rather than the conventional attempts to extract all pollutant molecules regardless of how tightly bound they are to the soil or sediment matrix. Initial work comparing SFE extraction behavior using mild to strong conditions with bioremediation behavior of PAHs shows great promise to develop extraction methodology to measure environmentally-relevant concentrations of pollutants in addition to their total concentrations.     

环境模拟样品中多环芳烃的超临界流体萃取I．利用正交设计选择最佳萃取条件

采用正交设计实验方法，研究了从环境模拟样品中超临界流体萃取（ＳＦＥ）多环芳烃（ＰＡＨ）的最佳萃取条件。着重考察了超临界流体的压力、温度和用量等对萃取效率的影响。结果表明，压力的影响居第一位，温度影响次之，超临界ＣＯ２的用量的影响居第三位。建立了选择超临界流体萃取条件的简单方法     

A cost effective,sensitive, and environmentally friendly sample preparation method for determination of polycyclic aromatic hydrocarbons in solid samples

A simple, cost effective, and yet sensitive sample preparation technique was investigated for determining Polycyclic Aromatic Hydrocarbons (PAHs) in solid samples. The method comprises ultrasonic extraction, Stir Bar Sorptive Extraction (SBSE), and thermal desorption–gas chromatography–mass spectrometry to increase analytical capacity in laboratories. This method required no clean-up, satisfied PAHs recovery, and significantly advances cost performance over conventional extraction methods, such as Soxhlet and Microwave Assisted Extraction (MAE). This study evaluated three operational parameters for ultrasonic extraction: solvent composition, extraction time, and sample load. A standard material, SRM 1649 a (urban dust), was used as the solid sample matrix, and 12 priority PAHs on the US Environmental Protection Agency (US EPA) list were analyzed. Combination of non-polar and polar solvents ameliorated extraction efficiency. Acetone/hexane mixtures of 2:3 and 1:1 (v/v) gave the most satisfactory results: recoveries ranged from 63.3% to 122%. Single composition solvents (methanol, hexane, and dichloromethane) showed fewer recoveries. Comparing 20 min with 60 min sonication, longer sonication diminished extraction efficiencies in general. Furthermore, sample load became a critical factor in certain solvent systems, particularly MeOH. MAE was also compared to the ultrasonic extraction, and results determined that the 20-min ultrasonic extraction using acetone/hexane (2:3, v/v) was as potent as MAE. The SBSE method using 20 mL of 30% alcohol-fortified solution rendered a limit of detection ranging from 1.7 to 32 ng L⁻¹ and a limit of quantitation ranging from 5.8 to 110 ng L⁻¹ for the 16 US EPA PAHs.     

Comparison of various extraction techniques for isolation and determination of isoflavonoids in plants

In the present paper, the following extraction techniques have been used for extracting isoflavonoids from the species Matricaria recutita, Rosmarinus officinalis, Foeniculum vulgare, and Agrimonia eupatoria L.: supercritical fluid extraction (SFE), pressurized fluid extraction, matrix solid phase dispersion, ultrasonic extraction in an ultrasonic bath (USE) and by means of an ultrasonic homogeniser (HOM), extraction by means of Soxhlet apparatus (SOX), and solid phase extraction. Experimental optimization of all techniques has been carried out using a soybean flour. Subsequent analyses of the extracts were carried out by liquid chromatography with UV detection. The maximum yields of daidzein and genistein were obtained by extraction with the SOX, USE, and HOM techniques. The maximum yields of apigenin and biochanin A from herb samples were obtained by SFE.     

SFE of PAHs from soils with a high carbon content and analyte collection via combined liquid/solid trapping

Polynuclear aromatic hydrocarbons (PAHs) are recovered from a soil with a high carbon content (ca. 50%) with supercritical fluid extraction (SFE) as well as with conventional Soxhlet extraction. The influence of temperature and modifier volume on SFE efficiency and the effect of a combined liquid/solid trap for analyte collection are investigated in this study. Such traps, which make analyte collection and clean-up possible in one step, are compared with conventional analyte collection in pure organic solvents. A comparison between reproducibility and efficiency of SFE and Soxhlet extraction is presented.     

Simultaneous extraction of di(2-ethylhexyl) phthalate and nonionic surfactants from house dust. Concentrations in floor dust from 15 Danish schools

Static extraction, supercritical fluid extraction (SFE), pressurized liquid extraction (PLE) and Soxhlet extraction were compared for simultaneous extraction of di(2-ethylhexyl) phthalate (DEHP) and nonionic surfactants from house dust. Homogenized office floor dust from a vacuum cleaner dust bag ("standard dust") was used for the evaluation. One portion of the extracts was used for analysis of nonionic surfactants with LC-MS and another portion was used for DEHP analysis with GC-MS. The extraction yield of DEHP was comparable for all the methods whereas SFE and PLE were the most efficient extraction techniques for the nonionic surfactants. The PLE extraction was found most suitable as a routine method for simultaneous extraction of both types of compounds and was used in a field study of floor dust from 15 Danish schools. The mean concentration of DEHP in the school dust samples was approximately 4 times higher than observed in other studies of dust from homes in different countries. The concentrations of nonionic surfactants were one order of magnitude lower than soap and linear alkylbenzene sulfonates measured in other studies of floor dust from offices and other public buildings. However, for the first time nonionic surfactants have been identified in house dust.     

Optimized Ultrasonic Extraction for the Determination of Polyaromatic Hydrocarbons by Gas Chromatography–Mass Spectrometry

The presence of polycyclic aromatic hydrocarbons (PAHs) in soil is an issue of concern due to their harmful effects on human health. The goal of this study was to optimize ultrasonic extraction to establish an efficient, easy, and low-cost method for the determination of 16 priority PAHs in soil. The time of extraction and solvent systems were optimized with the analysis by gas chromatography–mass spectrometry. The method was validated, and the optimum results were obtained using 1:1 cyclohexane:acetone and 1:1 hexane:acetone solvent systems with 30- and 60-min sonication times.     

凝固漂浮有机液滴-分散液液微萃取结合高效液相色谱法同时测定地表水中多环芳烃和酞酸酯

多环芳烃和酞酸酯是国际公认的优控污染物,因此准确快速地测定水中多环芳烃和酞酸酯非常重要。凝固漂浮有机液滴-分散液液微萃取（DLLME-SFO）是一种简便、快速、环境友好、灵敏度高的样品前处理技术。采用DLLME-SFO同时测定地表水中多环芳烃和酞酸酯的分析方法鲜有报道。该文采用凝固漂浮有机液滴-分散液液微萃取富集技术,结合高效液相色谱紫外/荧光法,建立了同时测定地表水中16种多环芳烃和6种酞酸酯的分析方法。考察优化了影响萃取效率的主要因素,包括萃取剂的种类和用量、分散剂的种类和用量、萃取时间和离子强度等。优化后的萃取实验条件为：5.0 mL水样,10 μL十二醇为萃取溶剂,500 μL甲醇为分散溶剂,涡旋振荡时间2 min,氯化钠用量0.2 g。目标化合物经多环芳烃专用色谱柱（SUPELCOSIL^TM LC-PAH,150 mm×4.6 mm,5 μm）结合乙腈-水梯度洗脱分离,16种多环芳烃除苊烯外采用荧光检测,苊烯和6种酞酸酯采用紫外检测,外标法定量。结果表明,22种目标化合物的基质加标回收率为60.2%~113.5%,相对标准偏差为1.9%~14.3%;多环芳烃和酞酸酯的检出限分别为0.002~0.07 μg/L和0.2~2.2 μg/L;多环芳烃和酞酸酯的定量限分别为0.006~0.23 μg/L和0.8~7.4 μg/L。该方法简便、快速,环境友好,灵敏度高,可用于地表水中多环芳烃和酞酸酯的快速分析检测。     

Efficiency of Different Methods and Solvents for the Extraction of Polycyclic Aromatic Hydrocarbons from Soils

The efficiencies of supercritical fluid extraction (SFE), accelerated solvent extraction (ASE), Soxhlet, and ultrasonic extraction in the analysis of polycyclic aromatic hydrocarbons (PAHs) in soils were evaluated. Solvents with different polarity were used to extract the PAHs from two soils, one with high and one with low contamination level. ASE showed good results with all solvents almost independent of the solvent polarity and the best results with acetone-toluene (1 : 1). Ultrasonic extraction with acetone-toluene for the uncontaminated soil and acetone-ethanolamine for the highly contaminated also showed good recoveries. The time-consuming Soxhlet extraction with pentane or dichloromethane was less effective. The PAH recovery from SFE was related to the soil matrix or the contamination level. The best extraction conditions (CO 2 /10% pentane) are successful for the soil with a low contamination level and a high humic acid content whereas the extractions of the highly contaminated soil gave poor results irrespective of the solvent used.     

Efficiency of supercritical fluid extraction for determining 4-nonylphenol in municipal sewage sludge.

When the sewage sludge containing the persistent, lipophilic, metabolite 4-nonylphenol (4-NP) has been disposed of in the environment it's toxic nature can lead to serious health risks to human beings and can also affect plants and aquatic organisms. Supercritical fluid extraction (SFE) is a new and powerful technique for extracting the organic contaminants from the solid phase. The present study was conducted to investigate optimal conditions for the quantitative extraction of 4-NP by SFE and to determine the concentration of 4-NP in municipal sewage sludge. The effect of several parameters such as temperature, pressure, static extraction time, dynamic extraction time, CO2 flow-rate, sample mass and modifier on the extraction were investigated. The optimal conditions for the extraction of the spiked sample were fluid pressure 97 bar, temperature 40 degrees C, flow-rate 3.0 ml/min, static extraction time 2 min, dynamic extraction time 5 min and modifier methanol (0.5 ml). Extracts were analyzed by gas chromatography-mass spectrometry. Concentration of 4-NP in the anaerobically degraded sludge of the De-Haw Sewage Treatment Plant in Taiwan was found to be 243.9 mg/kg. The extraction efficiency of the SFE method was compared with the conventional Soxhlet extraction method. The overall recovery of the SFE method was found to be greater and the results indicate that SFE is an efficient method for extracting 4-NP from sewage sludge.     

Quantitative determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides in sewage sludges using supercritical fluid extraction and mass spectrometric detection.

Supercritical CO2 extraction (SFE) proved to be a valuable, fast, quantitative and partly selective extraction technique for determining polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and chlorinated pesticides (OCPs) in sewage sludges of different catchment areas based on a comparison study with certified reference materials (CRMs) and on recovery data. Most PCB extracts could be measured directly after SFE whereas for PAHs a short clean-up improved the final separation by high-resolution capillary gas chromatography. Due to the amount of coextracted compounds and the low levels of OCPs, extracts obtained by SFE had to be submitted to a multistep clean-up for final measurement. Average concentrations of 6.9 mg/kg dry mass (dm) for the sum of the 16 Environmental Protection Agency PAHs, 0.1 mg/kg dm for the sum of the seven PCB congeners and 0.002-0.072 mg/kg dm for the OCPs were found in the sewage sludges. Compared to studies performed earlier in our laboratory PAHs are still present in similar concentrations whereas PCB levels have decreased significantly. OCPs could be detected in only low amounts. A correlation between sludge type and degree of contamination could only be found for PAHs.