Determination of PAHs in dust from Shanghai by optimized SFE and GC/MS

EPA 16 priority polycyclic aromatic hydrocarbons (PAHs) were extracted from dust by supercritical fluid extraction (SFE). Parameters (pressure, temperature and time) affecting the collection efficiencies of PAHs were assessed according to the extraction efficiency, and 30 MPa, 80 degrees C and 30 min dynamic extraction time were confirmed to be the best and simplest conditions of SFE to extract 16 priority PAHs from dust. The characterization of the extracts was carried out by gas chromatography with mass detector in selective ion mode (GC/MS/SIM). Ultrasonic extraction (USE) was used as a comparison with SFE. The results showed that the SFE method has a better efficiency than USE for the extraction of PAHs in dust. With the optimized conditions of SFE, the distribution of PAHs in dust samples in urban areas of Shanghai from Mar 10, 2005 to May 28, 2005 was investigated. The results demonstrated that traffic emission, especially from gasoline engines, was the main source of PAHs in dust of Shanghai.     

Accurate Quantification of Polycyclic Aromatic Hydrocarbons in Environmental Samples Using Deuterium-labeled Compounds as Internal Standards

For the accurate quantification of polycyclic aromatic hydrocarbons (PAHs) in environmental samples by isotope-dilution mass spectrometry (IDMS) and gas chromatography-mass spectrometry (GC-MS), we used deuterium-labeled PAHs (D-PAHs) as internal standards for microg g(-1)-level certified reference materials and corresponding calibration solutions. Although pressurized liquid extraction (PLE) causes significant biases in the analytical results for ng g(-1)-level samples (2.4 - 15%), biases in the analytical results by PLE (190 degrees C, 20 MPa, 2 cycles) were small (<2.3%) and negligible for microg g(-1)-level samples when expanded uncertainty (coverage factor k = 2) was considered.     

Optimisation of supercritical fluid extraction of polycyclic aromatic hydrocarbons and their nitrated derivatives adsorbed on highly sorptive diesel particulate matter

Supercritical fluid extraction (SFE) was performed to extract complex mixtures of polycyclic aromatic hydrocarbons (PAHs), nitrated derivatives (nitroPAHs) and heavy n-alkanes from spiked soot particulates that resulted from the incomplete combustion of diesel oils. This polluted material, resulting from combustion in a light diesel engine and collected at high temperature inside the particulate filter placed just after the engine, was particularly resistant to conventional extraction techniques, such as soxhlet extraction, and had an extraction behaviour that differed markedly from certified reference materials (SRM 1650). A factorial experimental design was performed, simultaneously modelling the influence of four SFE experimental factors on the recovery yields, i.e.: the temperature and the pressure of the supercritical fluid, the nature and the percentage of the organic modifier added to CO₂ (chloroform, tetrahydrofuran, methylene chloride), as a means to reach the optimal extraction yields for all the studied target pollutants. The results of modelling showed that the supercritical fluid pressure had to be kept at its maximum level (30 MPa) and the temperature had to be kept relatively low (75 °C). Under these operating conditions, adding 15% of methylene chloride to the CO₂ permitted quantitative extraction of not only light PAHs and their nitrated derivatives, but also heavy n-alkanes from the spiked soots. However, heavy polyaromatics were not quantitatively extracted from the refractory carbonaceous solid surface. As such, original organic modifiers were tested, including pyridine, which, as a strong electron donor cosolvent (15% into CO₂), was the most successful. The addition of diethylamine to pyridine, which enhanced the electron donor character of the cosolvent, even increased the extraction yields of the heaviest PAHs, leading to a quantitative extraction of all PAHs (more than 79%) from the diesel particulate matter, with detection limits ranging from 0.5 to 7.8 ng for 100 mg of spiked material. Concerning the nitrated PAHs, a small addition of acetic acid into pyridine, as cosolvents, gave the best results, leading to fair extraction yields (approximately 60%), with detection limits ranging from 18 to 420 ng.     

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.     

Solid-phase microextraction and headspace solid-phase microextraction for the determination of high molecular-weight polycyclic aromatic hydrocarbons in water and soil samples

The feasibility of direct-immersion (DI) solid-phase microextraction (SPME) and headspace (HS) SPME for the determination of high-ring polycyclic aromatic hydrocarbons (PAHs) (4- to 6-ring PAHs) in water and soil samples is studied. Three SPME fibers--100- and 30-microm polydimethylsiloxane (PDMS) and 85-microm polyacrylate (PA) fibers-are compared for the effective extraction of PAHs. Parameters affecting the sorption of PAHs into the fiber such as sampling time, sampling volume, and temperature are also evaluated. The extracted amounts of high-ring PAHs decrease with the decreasing of film thickness, and the 100-microm PDMS has the highest extraction efficiency than 85-microm PA and 30-microm PDMS fibers. Also, the extraction efficiency decreases with the increasing molecular weights of PAHs. Of the 10 high-ring PAHs, only fluoranthene and pyrene can reach equilibrium within 120 min at 25 degrees C for DI-SPME in a water sample. Increasing the temperature to 60 degrees C can increase the sensitivity of PAHs and shorten the equilibrium time. A 0.7- to 25-fold increase in peak area is obtained for DI-SPME when the working temperature is increased to 60 degrees C. For HS-SPME, the extraction efficiency of PAHs decrease when the headspace volume of the sampling system increases. All high-ring PAHs can be detected in a water sample by increasing the temperature to 80 degrees C. However, only 4- and 5-ring PAHs can be quantitated in a CRM soil sample when HS-SPME is used. The addition of a surfactant with high hydrophilic property can effectively enhance the sensitivity of high-ring PAHs. HS-SPME as well as DI-SPME with 100-microm PDMS or 85-microm PA fibers are shown to be suitable methods for analyzing high-ring PAHs in a water sample; however, this technique can only apply in a soil sample for PAHs having up to 5 rings.     

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.     

Development of a stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry method for the simultaneous determination of several persistent organic pollutants in water samples

Stir bar sorptive extraction (SBSE) and thermal desorption followed by capillary gas chromatography coupled to mass spectrometry (SBSE-TD-GC-MS) was applied to the simultaneous determination of ultra-traces of 16 polycyclic aromatic hydrocarbons (PAHs), 12 polychlorinated biphenyls (PCBs), 6 phthalate esters (PEs) and 3 nonylphenols (NPs) in water samples. The parameters that could affect the sorption-desorption efficiency were studied. A Plackett-Burman design was used for the screening of the main effects of the experimental parameters related to the desorption step (desorption time, desorption temperature, desorption flow, cryo-focusing temperature and vent pressure). Afterwards, two central composite designs were used to find the optimal process settings for the extraction and desorption steps. The best analytical compromise conditions for the simultaneous determination of analytes from spiked water samples were found to be: sample volume (20 mL), sodium chloride addition (30%), methanol addition (20%), desorption time (10 min), desorption temperature (300 degrees C), desorption flow (23 mL min(-1)), cryo-focusing temperature (-50 degrees C) and vent pressure (7 psi). Remarkable recovery, repeatability and reproducibility were attained. Furthermore, excellent linearities (r(2) = 0.959-0.999) and low detection limits (0.1-10 ng L(-1)) were also achieved for the congeners studied. The proposed methodology was applied for the simultaneous determination of PAHs, PCBs, PEs and NPs in sea and estuarine waters. The influence of humic acids on the recovery was also studied.     

MultiSimplex optimisation of the solid-phase microextraction-gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons,polychlorinated biphenyls and phthalates from water samples

Solid-phase microextraction coupled to GC-MS was optimised for the determination of polycyclic aromatic hydrocarbons (PAHs), phthalate esters and polychlorinated biphenyls (PCBs) in water samples. A 30-microm polydimethylsiloxane fiber was immersed in a 30-ml water sample that contained the analytes of interest (PAHs, PCBs and phthalate esters) and the variables studied were extraction time (15-60 min), extraction temperature (30-90 degrees C), desorption time (1-5 min), desorption temperature (220-270 degrees C) and the addition of sodium chloride (0-9 g). The MultiSimplex programme based on the simplex algorithm was used to establish the optimal conditions. MultiSimplex allowed the simultaneous study of the variables mentioned above and considered the answers of all types of compounds studied in this work. Thus, the optimal conditions obtained allowed the simultaneous determination of PAHs, phthalate esters and PCBs. Furthermore, the accuracy and repeatability of the developed method were calculated from water samples spiked at known concentrations of the analytes. Finally, the optimised method was used to analyse water samples from different sampling points of the Urdaibai and Nerbioi-Ibaizabal estuaries (Biscay, Spain).     

丹参中3种丹参酮的超临界二氧化碳萃取及液相分析

 用超临界CO2 流体及共溶剂乙醇萃取丹参中的 3种丹参酮 ,分别采用正交设计法和系统法考察了萃取中的主要影响因素 ;采用高效液相法 (HPLC) ,在甲醇 水 (体积比为 80∶2 0 )溶液为流动相和检测波长为 2 80nm的条件下 ,以外标法检测了萃取产物中 3种丹参酮的含量。实验得到的最佳条件为 :萃取压力 2 0MPa ;萃取温度 4 5℃ ;分离温度 35℃ ;共溶剂 95 % (体积分数 )乙醇 ;流量 1 0mL/min。建立的HPLC测定方法简便快捷 ,准确度高 ,重现性良好 ,相关系数r为 0 9994～ 0 9998,相对标准偏差RSD为 2 37%～ 3 4 7%。     

An aniline-based fiber coating for solid phase microextraction of polycyclic aromatic hydrocarbons from water followed by gas chromatography-mass spectrometry

A fiber coating from polyaniline (PANI) was electrochemically prepared and employed for solid phase microextraction (SPME) of some polycyclic aromatic hydrocarbons (PAHs) from water samples. The PANI film was directly electrodeposited on the platinum wire surface in sulfuric acid solution using cyclic voltammetry (CV) technique. The applicability of this coating was assessed employing a laboratory-made SPME device and gas chromatography with mass spectrometry (GC-MS) for the extraction of some PAHs from the headspace of aqueous samples. Application of wider potential range in CV led to a PANI with more stability against the temperature. The homogeneity and the porous surface structure of the film were examined by the scanning electron microscopy (SEM). The study revealed that this polymer is a suitable SPME fiber coating for extracting the selected PAHs. Important parameters influencing the extraction process were optimized and an extraction time of 40 min at 40 degrees C gave maximum peak area, when the aqueous sample was added with NaCl (20%, w/v). The synthesis of the PANI can be carried out conveniently and in a reproducible manner while it is rather inexpensive and stable against most of organic solvents. The film thickness of PANI can be precisely controlled by the number of CV cycles. The resulting thickness was roughly 20 microm after 20 cycles. At the optimum conditions, the relative standard deviation (RSD) for a double distilled water spiked with selected PAHs at ppb level were 8.80-16.8% (n = 3) and detection limits for the studied compounds were between 0.1-6 pg mL(-1). The performance of PANI was, also, compared with a commercial solid coated-based SPME fiber, carbowax/divinylbenzene (CW/DVB), under similar experimental conditions.     

An experimental design approach to optimise the determination of polycyclic aromatic hydrocarbons from rainfall water using stir bar sorptive extraction and high performance liquid chromatography-fluorescence detection

Stir bar sorptive extraction (SBSE) followed by HPLC-fluorescence detection (FLD) was optimised for analysing 15 polycyclic aromatic hydrocarbons (PAHs) from water samples, especially rainfall water with low PAH content. The literature data described widely different experimental conditions for the extraction of PAHs by SBSE. A chemometric approach was therefore used to evaluate the statistically influential and/or interacting factors, among those described in the literature, and to find the best extraction and desorption conditions. Among six factors studied in a 2(6-2) fractional factorial design, only sample volume, extraction time and the interaction between both of them had significant effects on the PAH extraction recoveries. Optimal sample volume of 10 mL and extraction time of 140 min were obtained with a response surface design. For the desorption conditions, a Box-Behnken design showed that desorption time, temperature and PAH concentrations had significant effects. The best conditions were two successive desorptions with 100 microL of acetonitrile for 25 min at 50 degrees C. The optimised method was repeatable (RSD< or =5.3% for 50 ng L(-1) spiked water and < or =12.8% for 5 ng L(-1) spiked water), linear (R(2)> or =0.9956), with quantitative absolute recoveries (> or =87.8% for 50 ng L(-1) spiked water), and with the LOD between 0.2 and 1.5 ng L(-1). The optimised method was successfully applied to six-rainfall water samples collected in a suburban area. The total PAHs concentrations studied ranged from 31 to 105.1 ng L(-1). Seasonal variation was observed and on average three PAHs were at the highest concentrations (phenanthrene, fluoranthene and pyrene).     

超临界二氧化碳萃取秋水仙碱（英文）

 利用超临界二氧化碳对秋水仙块根（经粉碎）中的秋水仙碱进行了萃取,采用高效液相色谱法对萃取出的秋水仙碱的质量分数进行了测定。实验选择40℃20～40MPa作为超临界苹取的操作条件,采用体积分数为95％的乙醇在索氏提取器中对样品进行了对比苹取实验。结果表明:不加浸泡剂进行浸泡处理的样品中的秋水仙碱很难被超临界二氧化碳萃取,在40℃,35MPa条件下,消耗1．28mol的二氧化碳只得到3％的萃取率。加入极少量的有机溶剂浸泡处理样品15min后再进行超临界萃取,可以极大程度地提高秋水仙碱的萃取率。     

Highly porous silica-polyaniline nanocomposite as a novel solid-phase microextraction fiber coating

A highly porous fiber-coated SBA-15/polyaniline material was prepared for solid-phase microextraction (SPME). The SBA-15/polyaniline nanocomposite was synthesized via chemical polymerization. The prepared SBA-15/polyaniline particles were analyzed by scanning electron microscopy analysis. The prepared nanomaterial was immobilized onto a stainless steel wire for fabrication of the SPME fiber. The fiber was evaluated for the extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions in combination with gas chromatography-mass spectrometry (GC-MS). In optimum conditions (extraction temperature 60°C, extraction time 40 min, ionic strength 20%, stirring rate: 500 rpm, desorption temperature 260°C, desorption time 2 min), the repeatability for one fiber (n=3), expressed as relative standard deviation (RSD%), was between 5.3 and 8.6% for the test compounds. For deionized water, spiked with selected PAHs, the detection limits for the studied compounds were between 2 and 20 pg/mL.     

Dynamic extraction in rotating coiled columns, a new approach to direct recovery of polycyclic aromatic hydrocarbons from soils

A new approach to the direct recovery of polycyclic aromatic hydrocarbons (PAHs) from environmental solid samples has been proposed. It has been shown that rotating coiled columns (RCCs) earlier used mainly in countercurrent chromatography can be successfully applied to the fast continuous-flow extraction of PAHs from soils. A particulate solid sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while a mixture of organic solvents (acetone-cyclohexane, 1:1, v/v) was continuously pumped through. The separation procedure requires less than half an hour, complete automation being possible. No clean-up step is needed before the subsequent HPLC- analysis of extracts. Besides, the dynamic multistage extraction performed in the rotating column at room temperature and normal pressure may have nearly the same efficiency as accelerated batch solvent extraction repeated three times at 150 degrees C and 14 MPa. Contents of PAHs in extracts obtained by using both methods are in good agreement with the certified data on the PAHs concentrations in the soil samples. The use of appropriate "mild" solvents for the dynamic extraction in rotating columns may be very perspective for the simulation of naturally occurring processes and determination of environmentally-relevant forms of PAHs and other pollutants in environmental solids. A particular emphasis could be placed on time-resolved (kinetic) studies of the mobilization of toxicants in soil systems.     

Factors Controlling Leaching of Polycyclic Aromatic Hydrocarbons from Petroleum Source Rock Using Nonionic Surfactant

The extraction of polycyclic aromatic hydrocarbons (PAHs) from petroleum source rock by nonionic surfactants with the assistance of microwave irradiation was investigated and the conditions for maximum yield were determined. The results showed that the extraction temperatures and type of surfactant have significant effects on extraction yields of PAHs. Factors such as surfactant concentration, irradiation power, sample/solvent ratio and mixing surfactants (i.e., mixture of surfactant at specific ratio) also influence the extraction efficiencies for these compounds. The optimum temperature for microwave-assisted nonionic surfactant extraction of PAHs from petroleum source rock was 120 °C and the best suited surfactant was Brij 35. The new method showed extraction efficiencies comparable to those afforded by the Soxhlet extraction method, but a reduction of the extraction times and environmentally friendliness of the new nonionic surfactant extraction system are clear advantages. The results also show that microwave-assisted nonionic surfactant extraction is a good and efficient green analytical preparatory technique for geochemical evaluation of petroleum source rock.

     

Simultaneous extraction of several persistent organic pollutants in sediment using focused ultrasonic solid-liquid extraction

Focused ultrasonic solid-liquid extraction (FUSLE) has been optimised for simultaneous analysis of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate esters (PEs), and nonylphenols (NPs) in sediment samples. Optimisation was performed using naturally polluted freeze-dried sediment samples. The variables studied during the optimisation process were: percentage of maximum power (10-60%), extraction time (10-300 s), number of cycles (1-9), composition of the extraction solvent (acetone-n-hexane, 10:90-90:10), and sample mass (0.1-1 g). The volume of the extractant was constant (10 mL) and the extraction was performed at 0 degrees C in an ice-bath during the optimisation process. All these variables were studied using an experimental design approach by means of The Unscrambler software. The extraction time and the operational variables (number of cycles and power) had no statistically significant effect in the extraction and they were held at 2 min, 20% power, and seven cycles, respectively. The mass and the addition of non-polar solvent (n-hexane) had a negative effect in the extraction yield and, thus, the mass was held at 0.5 g and pure acetone was used as extraction solvent. After those variables were optimised, the effect of the extraction temperature (0 degrees C or room temperature) was also studied. The validation of the extraction method was performed using NIST-1944 reference material in the case of PAHs and PCBs. Because no certified reference sediment is available for PEs and NPs, the results obtained for FUSLE were compared with those obtained for microwave-assisted extraction (MAE) under conditions optimised elsewhere. In all the cases the analysis were performed by gas chromatography-mass spectrometry (GC-MS). Good accuracy were achieved in all cases. The limits of detection (LODs) obtained were between 0.10 and 1.70 ng g(-1) for PAHs (except for naphthalene 5.33 ng g(-1)), 0.02 and 0.16 ng g(-1) for PCBs, 46 and 188 ng g(-1) for PEs, and 0.6 and 12.4 microg g(-1) for NPs. The precision was around 5-10% for most of the PAHs and PCBs and around 2-10% for most of the PEs and NPs.     

应用搅拌棒吸附萃取-热脱附-气相色谱/质谱法快速测定滇池水系中的16种多环芳烃

应用搅拌棒吸附萃取(SBSE)-热脱附(TDS)-气相色谱/质谱联用(GC/MS)方法测定了滇池水系(滇池和盘龙江上、中、下游)中16种多环芳烃(PAHs)的含量。方法快速简便,无有机溶剂污染,PAHs的最低检出限为1.0~468.8 pg,理论回收率在90%以上,加标回收率为83.1%~109.4%,相对标准偏差小于10%。测定结果表明,这16种多环芳烃在滇池水样中的含量为89.16 ng/L,在盘龙江上游水样中的含量为65.41 ng/L,在盘龙江中游水样中的含量为339.22 ng/L,而在盘龙江下游水样中的含量为62.25 ng/L,说明滇池水系已经受到一定的PAHs污染,加强对滇池、盘龙江中PAHs有机污染的控制势在必行。     

Inside needle capillary adsorption trap device for headspace solid-phase dynamic extraction based on polyaniline/hexagonally ordered silica nanocomposite

Highly porous polyaniline/hexagonally ordered silica sorbent was used for fabrication of the inside needle capillary adsorption trap (INCAT) device. Polyaniline/SBA-15 nanocomposite was synthesized via chemical polymerization technique. The fabricated INCAT device was evaluated to the extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions in combination with gas chromatography (GC)-mass spectrometry (MS). A one at-the-time optimization strategy was applied for optimizing the important extraction parameters such as extraction temperature, extraction time, ionic strength, sampling flow rate, desorption time, and desorption temperature. In optimum conditions (extraction temperature 55 °C, extraction time 20 min, ionic strength 20% (w/v), flow rate 4.5 mL min(-1), desorption temperature 270 °C, desorption time 3 min) the repeatability for one INCAT device (n = 4), expressed as relative standard deviation, was between 4.2 and 10.2% for the tested compounds. The quantitation limits for the studied compounds were between 1 and 5 pg mL(-1). The developed method was successfully applied to spring water sample which was spiked with PAHs with the relative recovery percentages of 87.3-109.1%. The developed method offers the advantage of being simple to use, with shorter analysis times, lower cost of equipment, and thermal stability.     

Pressurized liquid extraction of lipids for the determination of oxysterols in egg-containing food

Pressurized liquid extraction (PLE, ASE) was compared with the Folch procedure (a solid-liquid extraction with chloroform/methanol 2:1, v/v) for the lipid extraction of egg-containing food; the accuracy of PLE for the quantitative determination of oxysterols in whole egg powder was evaluated. Samples of spray-dried whole egg, an Italian vanilla cake (Pandoro) and egg noodles were used. Two different extraction solvents (chloroform/methanol 2:1, v/v, and hexane/isopropanol 3:2, v/v) were tested at different extraction temperatures and pressures (60 degrees C at 15 MPa, 100 degrees C at 15 MPa, 120 degrees C at 20 MPa). No significant differences in the lipid recovery of the egg powder sample using PLE were found. However, PLE of the vanilla cake and egg noodles with the chloroform/methanol mixture was not selective enough and led to the extraction of a non-lipid fraction, including nitrogen-containing compounds. In the same samples, the pressurized hexane/isopropanol mixture gave a better recovery result, comparable to that obtained using the Folch method. Cholesterol oxidation products of the Folch extract and the pressurized liquid extract of spray dried egg powder (obtained with hexane/isopropanol 3:2, v/v, at 60 degrees C and 15 MPa) were determined by gas chromatography. PLE performed under these conditions is suitable to replace the Folch extraction, because the differences between the two methods tested were not statistically significant. Moreover, PLE shows important advantages, since the analysis time was shortened by a factor of 10, the solvent costs were reduced by 80% and the use of chlorinated solvents was avoided.     

Systematic study of beta-asarone-rich volatile oil from Acori graminei rhizoma by off-line supercritical CO2 extraction-gas chromatography-mass spectrometry

Supercritical CO2 extraction (SCE) technology was used to extract a volatile oil, rich in beta-asarone, from Acori graminei rhizoma (AGR). The effect of different extraction and fractionation parameters on oil yield and selectivity towards beta-asarone was investigated by SCE using commercial AGR samples. The optimal conditions (P(e)/T(e) = 10 MPa/45 degrees C; P(f1)/T(f1) = 8 MPa/-10 degrees C; P(f2)/T(f2 )= 2 MPa/10 degrees C) gave a good oil yield and selectivity for beta-asarone. The extracts were also analyzed by GC-MS and compared with the volatile oil obtained by hydrodistillation, in which 39 main constituents including beta-asarone were found. Different cultivated AGR samples obtained from three areas of China were evaluated in terms of their volatile oil compositions obtained by extraction of commercial AGR samples under optimal conditions; the extract of the Guangdong (GD) sample showed a high beta-asarone content.