Determination of triazines in soil by microwave-assisted extraction followed by solid-phase microextraction and gas chromatography-mass spectrometry

A method for determining triazine herbicides in soil samples that combines microwave-assisted extraction with solid-phase microextraction is described. Water containing 1% methanol was employed as extractant. The parameters of solid-phase microextraction and microwave-assisted extraction were investigated. In solid-phase microextraction, particular attention was paid to the negative effect of salt on fiber stability. Our experiments showed that this effect could be effectively reduced by simply washing the fiber with deionized water. The selected triazines could be efficiently extracted by the aqueous extractant at 105 degrees C for 3 min, with 80% output of maximum power (1,200 W). The extraction procedure provided good precision (<7%) and recoveries (76.1-87.2%). The limits of detection were in the range 2-4 microg/kg. Compared with conventional liquid extraction, microwave-assisted extraction-solid-phase microextraction was more efficient, accurate and faster, and used a very small amount of organic solvent (only 250 microL methanol). The extraction of aged spiked soil samples indicated that, although the recoveries were lower than those of freshly spiked samples, they were nevertheless satisfactory for the quantitative analysis of real-world samples.     

Evaluation of solid-phase microextraction desorption parameters for fast GC analysis of cocaine in coca leaves

By its simplicity and rapidity, solid-phase microextraction (SPME) appears as an interesting alternative for sample introduction in fast gas chromatography (fast GC). This combination depends on numerous parameters affecting the desorption step (i.e., the release of compounds from the SPME fiber coating to the GC column). In this study, different liner diameters, injection temperatures, and gas flow rates are evaluated to accelerate the thermal desorption process in the injection port. This process is followed with real-time direct coupling a split/splitless injector to a mass spectrometer by means of a short capillary. It is shown that an effective, quantitative, and rapid transfer of cocaine (COC) and cocaethylene (CE) is performed with a 0.75-mm i.d. liner, at 280 degrees C and 4 mL/min gas flow rate. The 7-microm polydimethylsiloxane (PDMS) coating is selected for combination with fast GC because the 100-microm PDMS fiber presents some limitations caused by fiber bleeding. Finally, the developed SPME-fast GC method is applied to perform in less than 5 min, the quantitation of COC extracted from coca leaves by focused microwave-assisted extraction. An amount of 7.6 +/- 0.5 mg of COC per gram of dry mass is found, which is in good agreement with previously published results.     

The extraction and analysis of 1,4-dioxane from water using solid-phase microextraction coupled with gas chromatography and gas chromatography-mass spectrometry

In this study, two methods are developed for the extraction of 1,4-dioxane (dioxane) from water using 80-microm carboxen-polydimethylsiloxane solid-phase microextraction fibers followed by either gas chromatography (GC)-flame ionization detection (FID) or GC-mass spectrometry (MS). With GC-FID, the lower limit of detection (LOD) for 1,4-dioxane is 2.5 microg/L (ppb) with a linear range of 5 to 10,000 microg/L, obtained by immersing the fiber in the sample for 20 min with agitation. Using GC-MS, the lower limit of quantitation is 0.5 microg/L, and the LOD is 0.25 microg/L. The upper linear range limit is 100 microg/L. Samples are extracted in 20 min using either heated headspace with agitation or direct immersion with agitation.     

Determination of cocaine and cocaethylene in urine by solid-phase microextraction and gas chromatography-mass spectrometry

In order to evaluate recent cocaine exposure or its coingestion with ethanol, a simple and sensitive solid-phase microextraction (SPME) procedure for determination of cocaine and cocaethylene in urine was developed and validated. A polydimethylsiloxane fibre (100 microm) was submersed in the urine sample for 20 min under magnetic stirring after alkalinization with solid buffer (NaHCO(3):K(2)CO(3), 2:1). Gas chromatography-mass spectrometry (GC-MS) was used to identify and quantify the analytes in selected ion monitoring mode (SIM). The limits of quantification were 5.0 ng/mL for both analytes. Good inter- and intra-assay precision was also observed (coefficient of variation <9%).     

Determination of nonylphenol and octylphenol in paper by microwave-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry

A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography-mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25-125 microg kg(-1) for OP and 9.50-950 microg kg(-1) for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56 microg kg(-1) for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211 microg kg(-1).     

Extraction and analysis of different Cannabis samples by headspace solid-phase microextraction combined with gas chromatography-mass spectrometry

A headspace solid-phase microextraction combined with GC-MS method was developed for the extraction and analysis of cannabinoids from Cannabis samples. Different commercially available fibres were evaluated; polydimethylsiloxane 100 microm was selected as the most efficient one. In order to enhance sensitivity and reduce analysis time, the sampling temperature was studied and it showed that extraction should be performed at a high temperature (150 degrees C). In relation with the high lipophilicity of cannabinoids, a relatively long desorption time (3 min) was necessary to ensure a total transfer from the fibre into the injection port of the gas chromatograph. The method was finally applied to the extraction of Swiss marijuana samples from different regions. Data treatment by principal component analysis and hierarchical cluster analysis allowed a discrimination of the different batches.     

Two-fibre solid-phase microextraction combined with gas chromatography-mass spectrometry for the analysis of volatile aroma compounds in cooked pork

The volatile aroma compounds in cooked pork were examined using solid-phase microextraction (SPME). Two SPME fibres coated with different stationary phases were used simultaneously to collect aroma compounds from the headspace above the pork. One fibre was coated with 75 microm. Carboxen-polydimethylsiloxane and the other was coated with 50/30 microm divinylbenzene-Carboxen on polydimethylsiloxane. After extraction, the two fibres were desorbed in the injection port of a gas chromatograph sequentially, so that the aroma compounds from both of the fibres could be analysed in one gas chromatogram. This procedure resulted in a chromatogram containing a more complete aroma profile for cooked pork than the chromatograms from either of the fibres on their own. Thirty-six compounds were identified in cooked pork for the first     

Determination of additives in cosmetics by supercritical fluid extraction on-line headspace solid-phase microextraction combined with gas chromatography-mass spectrometry

A new hyphenated technique couples supercritical fluid extraction in situ derivatization and on-line headspace solid-phase microextraction to gas chromatography-mass spectrometry (SFE in situ derivatization on-line HS-SPME-GC-MS) for the determination of paraben preservatives and polyphenolic antioxidants in cosmetics. The preservatives and antioxidants were extracted from the cosmetic matrices with supercritical carbon dioxide at a pressure of 13,840 kPa. The supercritical fluid extraction was performed at 55 °C for 10 min of static extraction then 15 min of dynamic extraction. The extractant subsequently was derivatized in situ with the silylation reagent N,O-bis(trimethylsilyl)trifluoroacetamide with 0.1% trimethylchlorosilane. The product was then adsorbed on a polyacrylate solid-phase microextraction (SPME) fiber in the headspace. Sea sand was used as a dispersive material in the SFE step. The analytical linear ranges for the preservatives and antioxidants were found to be from 10 to 1000 ng g⁻¹ with RSD values below 7.8%. The detection limits ranged from 0.5 to 8.3 ng g⁻¹. These results are better than those obtained by using only SPME or SFE for trace preservatives and antioxidants analysis in cosmetic matrices. The new method was successfully utilized to determine the amounts of preservatives and antioxidants in real cosmetics without the need for tedious pretreatments.     

Determination of volatile compounds in Magnolia bark by microwave-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry.

A method is described for the determination of volatile compounds in Magnolia bark using microwave-assisted extraction coupled to headspace solid-phase microextraction (MAE-HS-SPME), followed by gas chromatography with mass spectrometry (GC-MS). Parameters affecting the extraction efficiency, such as sampling time and temperature, microwave irradiation power and desorption time, were investigated to achieve the optimal conditions. The result obtained was compared with that of steam distillation; only small differences existed between these two methods. Therefore, the proposed method seems to be a feasible and relatively simple, fast and solvent-free procedure for identification of essential oils in Magnolia bark.     

Determination of synthetic polycyclic musks in water by microwave-assisted headspace solid-phase microextraction and gas chromatography-mass spectrometry

This paper describes a rapid and solvent-free method, microwave-assisted headspace solid-phase microextraction (MA-HS-SPME), for the extraction of six commonly used synthetic polycyclic musks: galaxolide (HHCB), tonalide (AHTN), celestolide (ADBI), traseolide (ATII), cashmeran (DPMI) and phantolide (AHMI) from water samples prior to their determination using gas chromatography-mass spectrometry (GC-MS). The effects of various extraction parameters for the quantitative extraction of these analytes by MA-HS-SPME were systematically investigated and optimized. The analytes in a 20-mL water sample (in a 40-mL sample-vial containing 4 g of NaCl) were efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the system was microwave irradiated at 180 W for less than 4 min. The limits of detection (LODs) ranged from 0.05 to 0.1 ng/L, and the limits of quantification (LOQs) were less than 0.2 ng/L. A preliminary analysis of wastewater samples revealed that HHCB and AHTN were the two most commonly detected synthetic polycyclic musks; using a standard addition method, their concentration were determined to range from 1.2 to 37.3 ng/L with relative standard deviation (RSD) ranging from 2 to 6%. The results obtained using this approach are better than those from the conventional oil-bath HS-SPME.     

Rapid determination of paeonol in traditional Chinese medicinal preparations by microwave-assisted extraction followed by headspace solid-phase microextraction and gas chromatography-mass spectrometry

Microwave-assisted extraction (MAE) followed by headspace solid-phase microextraction (HS-SPME) was developed for rapid determination of paeonol in four traditional Chinese medicinal preparations (TCMPs) including Liuwen Dihuang pills, Maiwei Dihuang pills, Guifu Dihuang pills, and Zhibai Dihuang pills. The optimal MAE conditions obtained were: microwave power of 540 W and irradiation time of 4 min, and HS-SPME optimal conditions were: fiber coating of 65 μm PDMS/DVB, extraction temperature of 70°C, extraction time of 10 min, stirring rate of 1100 rpm, and NaCl concentration 30%. The optimized method provided satisfactory precision (RSD 6.5%), good linearity (R ₂ > 0.997) and recovery (90%). The results showed that MAE-HS-SPME-GC-MS is a simple, rapid, efficient, and solvent-free technique for the quantitative determination of paeonol in TCMPs.     

Development of microwave-assisted extraction followed by headspace solid-phase microextraction and gas chromatography-mass spectrometry for quantification of camphor and borneol in Flos Chrysanthemi Indici

In the work, microwave-assisted extraction (MAE) followed by headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) was developed for quantitative analysis of the bioactive components of camphor and borneol in a traditional Chinese medicines (TCM) of Flos Chrysanthemi Indici. After systematical investigation, the optimal experimental parameters microwave power (400 W), irradiation time (4 min), fiber coating (PDMS/DVB fiber), extraction temperature (40 °C), extraction time (20 min), stirring rate (1100 rpm), and salt effect (no salt added) were investigated. The optimized method provided satisfactory precision (RSD values less than 12%), good recovery (from 86% to 94%), and good linearity (R² > 0.999). The proposed method was applied to quantitative analysis of camphor and borneol in Flos Chrysanthemi Indici samples from 11 different growing areas. To demonstrate the method feasibility, steam distillation was also used to analyze camphor and borneol in Flos Chrysanthemi Indici samples from these different growing areas. The very close results were obtained by the two methods. It has been shown that the proposed ME-HS-SPME-GC-MS is a simple, rapid, solvent-free and reliable method for quantitative analysis of camphor and borneol in TCM, and a potential tool for quality assessment of Flos Chrysanthemi Indici.     

Purge-assisted headspace solid-phase microextraction combined with gas chromatography-mass spectrometry for determination of chlorophenols in aqueous samples

A simple, economical and very effective method is demonstrated for simultaneous determination of 2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol, in aqueous samples, by using purge-assisted headspace solid-phase microextraction (PA/HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS). In the new method, purging the sample enhances the removal of the trace chlorophenols without derivatization from the matrices to the headspace. Extraction parameters including extraction temperature, purge gas flow rate and extraction time were systematically investigated. Under optimal conditions, the relative standard deviations (RSDs) were 4-11% at 50 pg/mL and 5-14% at 5 pg/mL, respectively. The recoveries were in the range of 83-114%. Detection limits were determined at the fg level. These results indicate that PA/HS-SPME provides a significant contribution to highly efficient extraction of semi-volatile CPs, especially for pentachlorophenol, which has the smallest Henry's constant and large octanol-water partitioning coefficient. In addition, the proposed method was successfully applied to the analysis of chlorophenols in landfill leachate. New perspectives are opened for headspace extraction of relatively low vapor pressure compounds in complex matrices.     

Determination of fipronil by solid-phase microextraction and gas chromatography-mass spectrometry.

A method for the determination of trace amounts of the insecticide fipronil was developed using solid-phase microextraction-gas chromatography-mass spectrometry and selected ion monitoring. Fipronil was extracted with a fused-silica fiber coated with 85 microm polyacrylate. The effects of pH, ionic strength, sample volume, extraction and desorption times as well as the extraction temperature were studied. Lindane was used as an internal standard. The linear concentration range of application was 0.3-100 ng ml(-1) of fipronil, with a relative standard deviation of 9.5% (for a level of 50 ng ml(-1)) and a detection limit of 0.08 ng ml(-1). The method was applied to check the eventual existence of fipronil above this limit in water and soil samples from Granada (Spain) as well as in human urine samples. The method validation was completed with spiked matrix samples. The method can be applied as a monitoring tool for water, soil and urine, in the investigation of environmental and occupational exposure to fipronil.     

Quantitative analysis of acetates in cigarette tobacco using solid-phase microextraction and gas chromatography-mass spectrometry

A method incorporating solid-phase microextraction (SPME) and gas chromatography-mass spectrometry for the headspace analysis of selected volatile organic compounds present in cigarette tobacco is developed and evaluated. Quantitative information on methyl, ethyl, n-propyl, isopropyl, isopropenyl, vinyl, and butyl acetates present in 29 different flavor variants (full, light, and ultra-light) of the top ten selling brands in the United States is presented. The concentrations of the various acetate analytes range from the low nanaogram to microgram levels per cigarette. Clear differences are observed in the concentrations of various acetates when comparing the levels in brands from different manufacturers. The SPME technique provides a method that allows high sample throughput, requires little sample preparation, and yields useful analytical information. High precision is obtained on multiple measurements of cigarettes from an individual pack, but lower precision levels are observed in general when comparing results obtained on the analysis of cigarettes from different packs of the same brand. The higher pack-to-pack variations may be due in part to product aging with a proportionate amount of evaporative loss of the relatively volatile acetates.     

Determination of tebufenpyrad and oxadiazon by solid-phase microextraction and gas chromatography-mass spectrometry

Summary A method for determination of trace amounts of the pesticides tebufenpyrad and oxadiazon, previous solid-phase microextraction (SPME), was developed using gas chromatographymass spectrometry and selected ion monitoring (GC-MS; SIM). Both pesticides were extracted with a fused silica fiber coated with 100 μm polydimethylsiloxane. The effects of pH ionic strength, sample volume, extraction and desorption times as well as extraction temperature were studied. The linear concentration range of application was 0.5–250 ng mL⁻¹ for both compounds, with a detection limit of 0.06 ng mL⁻¹ for tebufenpyrad and 0.02 ng mL⁻¹ for oxadiazon. SPME-GC-MS analysis yielded good reproducibility (RSD between 7.5–10.1%). It was used to check the eventual existence of tebufenpyrad and oxadiazon above this limit in water and soil samples from Granada (Spain) as well as in human urine samples. The method validation was completed with spiked matrix samples. It can be applied as a monitoring tool for water, soil and urine in the investigation of environmental and occupational exposure to tebufenpyrad and oxadiazon.     

Determination of oxadiazon residues by headspace solid-phase microextraction and gas chromatography-mass spectrometry

A method for the determination of trace amounts of the herbicide oxadiazon was developed using headspace solid-phase microextraction (HS-SPME), gas chromatography-mass spectrometry (GC-MS) and selected ion monitoring. It was applied to determine oxadiazon in ground water, agricultural soil, must, wine and human urine samples. To determine oxadiazon in liquid samples, a response surface methodology generated with a Doehlert design was applied to optimize the HS-SPME conditions using a 100 microm polydimethylsiloxane fibre. For the analysis of soil samples, they were mixed with water and the SPME fibre suspended in the headspace above the slurry. Ground water, human urine and must show linear concentration range of application of 0.5-50 ng ml(-1)' with detection limits < or =0.02 ng ml(-1). HS-SPME-GC-MS analysis yielded good reproducibility (RSD values between 6.5 and 13.5%). The method validation was completed with spiked matrix samples. The developed analytical procedure is solvent free, cost effective and fast.     

Analysis of unknown organic pollutants in sewage by solid-phase extraction combined with gas chromatography-mass spectrometry

A rapid, simple, and reliable method of solid-phase extraction (SPE) combined with gas chromatography (GC)-mass spectrometry (MS) is developed for the analysis of a wide range of polarity of unknown organic pollutants in sewage. Wastewater samples are extracted by passing them through disposable C(18) cartridges, and the extracts are then analyzed by GC-MS. Different SPE parameters for ten organic compounds in the list of priority pollutants suggested by the China Environmental Protection Agency (EPA) are studied, and their breakthrough volumes are determined. Extraction recoveries for the tested compounds are greater than 60%, except the recovery of 1,2-dichloroethane is 48%. The relative standard deviations are less than 7.8% (n = 3). The developed approach is successfully applied for the identification of organic components in a sewage sample. Over 220 organic pollutants are identified, with 5 of these present in the list of priority pollutants suggested by the U.S. EPA and 4 from the list by the China EPA.