Rapid determination of the volatile components in tobacco by ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction with gas chromatography‐mass spectrometry

An ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction was first employed to determine the volatile components in tobacco samples. The method combined the advantages of ultrasound, microwave, and headspace solid‐phase microextraction. The extraction, separation, and enrichment were performed in a single step, which could greatly simplify the operation and reduce the whole pretreatment time. In the developed method, several experimental parameters, such as fiber type, ultrasound power, and irradiation time, were optimized to improve sampling efficiency. Under the optimal conditions, there were 37, 36, 34, and 36 components identified in tobacco from Guizhou, Hunan, Yunnan, and Zimbabwe, respectively, including esters, heterocycles, alkanes, ketones, terpenoids, acids, phenols, and alcohols. The compound types were roughly the same while the contents were varied from different origins due to the disparity of their growing conditions, such as soil, water, and climate. In addition, the ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction method was compared with the microwave‐assisted extraction coupled to headspace solid‐phase microextraction and headspace solid‐phase microextraction methods. More types of volatile components were obtained by using the ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction method, moreover, the contents were high. The results indicated that the ultrasound‐microwave synergistic extraction coupled to headspace solid‐phase microextraction technique was a simple, time‐saving and highly efficient approach, which was especially suitable for analysis of the volatile components in tobacco.     

Use of volatile organic solvents in headspace liquid‐phase microextraction by direct cooling of the organic drop using a simple cooling capsule

A low‐cost and simple cooling‐assisted headspace liquid‐phase microextraction device for the extraction and determination of 2,6,6‐trimethyl‐1,3 cyclohexadiene‐1‐carboxaldehyde (safranal) in Saffron samples, using volatile organic solvents, was fabricated and evaluated. The main part of the cooling‐assisted headspace liquid‐phase microextraction system was a cooling capsule, with a Teflon microcup to hold the extracting organic solvent, which is able to directly cool down the extraction phase while the sample matrix is simultaneously heated. Different experimental factors such as type of organic extraction solvent, sample temperature, extraction solvent temperature, and extraction time were optimized. The optimal conditions were obtained as: extraction solvent, methanol (10 μL); extraction temperature, 60°C; extraction solvent temperature, 0°C; and extraction time, 20 min. Good linearity of the calibration curve (R² = 0.995) was obtained in the concentration range of 0.01–50.0 μg/mL. The limit of detection was 0.001 μg/mL. The relative standard deviation for 1.0 μg/mL of safranal was 10.7% (n = 6). The proposed cooling‐assisted headspace liquid‐phase microextraction device was coupled (off‐line) to high‐performance liquid chromatography and used for the determination of safranal in Saffron samples. Reasonable agreement was observed between the results of the cooling‐assisted headspace liquid‐phase microextraction high‐performance liquid chromatography method and those obtained by a validated ultrasound‐assisted solvent extraction procedure.     

Sensitive determination of polychlorinated biphenyls in environmental water samples by headspace solid‐phase microextraction with bamboo charcoal@iron oxide black fibers prior to gas chromatography with tandem mass spectrometry

We have investigated the feasibility of bamboo charcoal@iron oxide black for the headspace solid‐phase microextraction of polychlorinated biphenyls in environmental water samples. Bamboo charcoal@iron oxide black was prepared and used as a solid‐phase microextraction coating material, and gas chromatography with tandem mass spectrometry was used for detection. Several important factors affecting the extraction efficiency were systematically investigated and optimized. Under the optimum conditions, the experimental data exhibited wide linear range over the range 0.2–1000 ng/L and low limits of detection in the range of 4.7–22.2 pg/L. The novel coating was successfully used for the enrichment and determination of polychlorinated biphenyls in real environmental water samples. All these results indicated that bamboo charcoal@iron oxide black‐based headspace solid‐phase microextraction coupled to gas chromatography with tandem mass spectrometry was an excellent alternative for the sensitive analysis of polychlorinated biphenyls at ultratrace levels in the environment.     

Geographical discrimination of Chinese winter wheat using volatile compound analysis by HS‐SPME/GC‐MS coupled with multivariate statistical analysis

This study aimed to develop a potential analytical method to discriminate the Chinese winter wheat according to geographical origin and cultivars. A total of 90 wheat samples of 10 different wheat cultivars among three regions were examined by headspace solid phase microextraction coupled with gas chromatography‐mass spectrometry (GC‐MS). The peak areas of 32 main volatile compounds were selected and subjected to statistical analysis, which revealed significant differences among different regions and cultivars. Multivariate analysis of variance showed a significant influence of regions, wheat genotypes, and their interaction on the volatile composition of wheat. Principal component analysis of the aromatic profile showed better visualization for wheat geographical origins. Finally, a classification model based on the linear discriminant analysis was successfully constructed for the discrimination of regions and cultivars with the correct classification percentages of 90 and 100%, respectively.     

Exploring multiple‐cumulative trapping solid‐phase microextraction for olive oil aroma profiling

Headspace solid‐phase microextraction is a solvent‐free sample preparation technique that is based on the equilibrium among a three‐phase system, i.e., sample‐headspace‐fiber. A compromise between sensitivity and extraction time is usually needed to optimize the sample throughput, especially when a large number of samples are analyzed, as usually the case in cross‐samples studies. This work explores the capability of multiple‐cumulative trapping solid‐phase microextraction on the characterization of the aroma profiling of olive oils, exploiting the automation capability of a novel headspace autosampler. It was shown that multiple‐cumulative solid‐phase microextraction has the potential to improve the overall sensitivity and burst the level of information for cross‐sample studies by using cumulative shorter extraction times.     

Exploiting the versatility of vacuum‐assisted headspace solid‐phase microextraction in combination with the selectivity of ionic liquid‐based GC stationary phases to discriminate Boswellia spp. resins through their volatile and semivolatile fractions

The frankincense resins, secreted from Boswellia species, are an uncommon example of a natural raw material where every class of terpenoids is present in similar proportions. Diterpenoids (serratol, incensole, and incensole acetate) are used to discriminate samples from different species and origins. Headspace solid‐phase microextraction has been used for frankincense analysis, although it requires long sampling time for medium‐ to low‐volatility markers; headspace solid‐phase microextraction under vacuum can overcome this limit. Gas chromatography is used for analysis but the separation of incensole and serratol needs polar stationary phases. In this study, we develop a method to discriminate frankincenses based on vacuum‐assisted headspace solid‐phase microextraction combined with fast gas chromatography‐mass spectrometry with ionic liquid–based stationary phases. The optimized conditions for solid samples were: air evacuation below 0°C, 15 min of incubation time, and 15 min of extraction time. Losses of volatiles due to vial air‐evacuation in the presence of the sample were minimized by sample amount above 100 mg and low sample temperature. Fast gas chromatography provides the baseline separation of all markers in 20 min. By applying vacuum sampling and fast gas chromatography, the total analysis was reduced to 50 min compared to 120 min (60 min sampling plus 60 min analysis) as previously reported. The method was successfully applied to commercial frankincense samples.     

A Microwave‐assisted Headspace Solid‐phase Microextraction for Rapid Determination of Synthetic Polycyclic and Nitro‐aromatic Musks in Fish Samples

Rapid solvent‐free microwave‐assisted headspace solid‐phase microextraction (MA‐HS‐SPME) coupled with gas chromatography‐mass spectrometry (GC‐MS) was developed to determine synthetic polycyclic and nitro‐aromatic musks in fish samples. Four commonly used synthetic musks, galaxolide (HHCB), tonalide (AHTN), musk xylene (MX) and musk ketone (MK) were employed in the method development and validation. The parameters (microwave irradiation time, irradiation power, amount of water addition, pH value and addition of NaCl) affecting the extraction efficiency of analytes from fish slurry were systematically investigated and optimized. The best extraction conditions were achieved when the fish sample 2‐g mixed with 4‐mL methanol and 15‐mL deionized water (containing 4 g of NaCl, pH 2.0 in a 40‐mL sample‐vial) was microwave irradiated at 80 watt for 5 min. The limits of quantification (LOQ) were 0.4 to 1.2 ng/g in 2‐g of wet tissue. The precision for these analytes, as indicated by relative standard deviations, were less than 9% for both intra‐ and inter‐day analysis. Accuracy, expressed as the mean extraction recovery, was between 80 to 92%. A standard addition method was used to quantitate these four synthetic musks, and the total concentrations ranged from 2.1 to 23.1 ng/g in various fish samples.     

Comparison of headspace solid‐phase microextraction and solvent extraction method for the simultaneous analysis of various soil fumigants in soil or water by gas chromatography–mass spectrometry

The quantity of soil fumigants has increased globally that has focused attention on their environmental behavior. However, simultaneous analysis of traces of fumigant residues is often unreported because analysis methods are not readily available to measure them at low concentrations. In this study, typical solvent extraction methods were compared with headspace solid‐phase microextraction methods. Both methods can be used for simultaneously measuring the concentrations of five commonly used soil fumigants in soil or water. The solvent extraction method showed acceptable recovery (76–103%) and intraday relative standard deviations (0.8–11%) for the five soil fumigants. The headspace solid‐phase microextraction method also showed acceptable recovery (72–104%) and precision rates (1.3–17%) for the five soil fumigants. The solvent extraction method was more precise and more suitable for analyzing relatively high fumigant residue levels (0.05–5 μg/g) contained in multiple soil samples. The headspace solid‐phase microextraction method, however, had a much lower limits of detection (0.09–2.52 μg/kg or μg/L) than the solvent extraction method (5.8–29.2 μg/kg), making headspace solid‐phase microextraction most suitable for trace analysis of these fumigants. The results confirmed that the headspace solid‐phase microextraction method was more convenient and sensitive for the determination of fumigants to real soil samples.     

Determination of volatile organic acids in tobacco by single‐drop microextraction with in‐syringe derivatization followed by GC‐MS

In this work, the novel technique based on headspace single‐drop microextraction with in‐syringe derivatization followed by GC‐MS was established to determine the volatile organic acids in tobacco. The parameters for headspace single‐drop microextraction and in‐syringe derivatization were optimized, including extraction time, and volume of derivatization reagent and in‐syringe derivatization time. The method validations including linearity, precision, recovery and LOD were also studied. The obtained results illustrated that the optimized technique was easy, highly efficient and sensitive. Finally, the proposed method was successfully applied to the analyses of volatile organic acids in tobacco samples with seven different brands. It was further demonstrated that the present technique developed in this study does offer a simple and fast approach to determine volatile organic acids in tobacco.     

Development of a Sensitive Method for the Determination of 4‐(Methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol in Human Urine Using Solid‐phase Extraction Combined with Ultrasound‐assisted Dispersive Liquid–liquid Microextraction and LC‐MS/MS Detection

An efficient and sensitive analytical method based on molecularly imprinted solid‐phase extraction (MISPE) and reverse‐phase ultrasound‐assisted dispersive liquid–liquid microextraction (USA‐DLLME) coupled with LC–MS/MS detection was developed and validated for the analysis of urinary 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a tobacco‐specific nitrosamine metabolite. The extraction performances of NNAL on three different solid‐phase extraction (SPE) sorbents including the hydrophilic‐lipophilic balanced sorbent HLB, the mixed mode cationic MCX sorbent and the molecularly imprinted polymers (MIP) sorbent were evaluated. Experimental results showed that the analyte was well retained with the highest extraction recovery and the optimum purification effect on MIP. Under the optimized conditions of MIP and USA‐DLLME, an enrichment factor of 23 was obtained. Good linearity relationship was obtained in the range of 5‐1200 pg/mL with a correlation coefficient of 0.9953. The limit of detection (LOD) was 0.35 pg/mL. The recoveries at three spiked levels ranged between 88.5% and 93.7%. Intra‐ and inter‐day relative standard deviations varied from 3.6% to 7.4% and from 5.4% to 9.7%, respectively. The developed method combing the advantages of MISPE and DLLME significantly improves the purification and enrichment of the analyte and can be used as an effective approach for the determination of ultra‐trace NNAL in complex biological matrices.     

Improvement of solid‐phase microextraction efficiency by the application of a carbon‐nanotubes‐based ternary microextraction fiber composite

In this study, a novel technique is proposed for preparation of an efficient and unbreakable metal‐wire‐supported solid‐phase microextraction fiber. A sol–gel film was deposited on electrophoretically deposited carbon nanotubes on a stainless‐steel wire. The applicability of the fiber was evaluated through the extraction of some aromatic pollutants as model compounds from the headspace of aqueous samples in combination with gas chromatography and mass spectrometry. The parameters affecting the structure and extraction efficiency of the fiber (including the type of solvent, time, and potential for electrophoretic deposition) and the parameters affecting the extraction efficiency (such as coating type, salt content, extraction temperature, and time) were investigated. The results showed that the film thickness will be increased by increasing the potential and time duration. Finally, the characterization of the deposited film was accomplished by scanning electron microscopy and thermogravimetric analysis. After the optimization of the extraction parameters, the limit of detection of less than 20 pg/mL was achieved, and the calibration curves were all linear (r ² ≥ 0.9737), in the range from 50 to 500 pg/mL. The solid‐phase microextraction fiber has a high mechanical strength; good stability and long service life, making it potentially applicable in the extraction of trace polycyclic aromatic hydrocarbons from aqueous samples.     

Electro‐assisted solid‐phase microextraction based on poly(3,4‐ethylenedioxythiophen) combined with GC for the quantification of tricyclic antidepressants

In this study, a platinum wire coated with poly(3,4‐ethylenedioxythiophen) was used as an electro‐assisted solid‐phase microextraction fiber for the quantification of tricyclic antidepressant drugs in biological samples by coupling to GC employing a flame ionization detector. In this study, an electric field increased the extraction rate and recovery. The fiber used as a solid phase was synthesized by the electropolymerization of 3,4‐ethylenedioxythiophen monomers onto a platinum wire. The ability of this fiber to extract imipramine, desipramine, and clomipramine by using the electro‐assisted solid‐phase microextraction technique was evaluated. The effect of various parameters that influence the extraction efficiency, which include solution temperature, extraction time, stirring rate, ionic strength, time and temperature of desorption, and thickness of the fiber, was optimized. Under optimized conditions, the linear ranges and regression coefficients of calibration curves were in the range of 0.5–250 and 0.990–0.998 ng/mL, respectively. Detection limits were in the range of 0.15–0.45 ng/mL. Finally, this method was applied to the determination of drugs in urine and wastewater samples and recoveries were 4.8–108.9%.     

Analysis of volatile oil composition of Citrus aurantium L. by microwave‐assisted extraction coupled to headspace solid‐phase microextraction with nanoporous based fibers

Nanoporous silica was prepared and functionalized with amino propyl‐triethoxysilane to be used as a highly porous fiber‐coating material for solid‐phase microextraction (SPME). The prepared nanomaterials were immobilized onto a stainless steel wire for fabrication of the SPME fiber. The proposed fiber was evaluated for the extraction of volatile component of Citrus aurantium L. leaves. A homemade microwave‐assisted extraction followed by headspace (HS) solid‐phase apparatus was used for the extraction of volatile components. For optimization of factors affecting the extraction efficiency of the volatile compounds, a simplex optimization method was used. The repeatability for one fiber (n = 4), expressed as RSD, was between 3.1 and 8.6% and the reproducibility for five prepared fibers was between 10.1 and 14.9% for the test compounds. Using microwave‐assisted distillation HS‐SPME followed by GC‐MS, 53 compounds were separated and identified in C. aurantium L., which mainly included limonene (62.0%), linalool (7.47%), trans‐β‐Ocimene (3.47%), and caryophyllene (2.05%). In comparison to a hydrodistillation method, the proposed technique could equally monitor almost all the components of the sample, in an easier way, which was rapid and required a much lower amount of sample.     

Automated headspace solid‐phase microextraction and on‐fiber derivatization for the determination of clenbuterol in meat products by gas chromatography coupled to mass spectrometry

A method was developed for the determination of clenbuterol in meat using stable‐isotope‐dilution gas chromatography with mass spectrometry coupled with solid‐phase microextraction and on‐fiber derivatization. The samples were first homogenized with hydrochloric acid followed by protein deposition. After headspace solid‐phase microextraction and on‐fiber derivatization, the content of clenbuterol was measured with the aid of stable‐isotope dilution. The condition of solid‐phase microextraction was optimized by central composite design. The relative standard deviations, limit of detection, and recoveries for clenbuterol were 4.2–9.2%, 0.48 μg/kg, and 96–104%, respectively. The proposed method was satisfactory for analysis of real samples as compared with the Chinese standard method.     

Inhibiting sorbent stripping by designing a sorbent‐packed porous probe for headspace solid‐phase microextraction

To prevent the stripping of coating sorbents in headspace solid‐phase microextraction, a porous extraction probe with packed sorbent was introduced by using a porous stainless steel needle tube and homemade sol–gel sorbents. The traditional stainless‐steel needle tube was punched by a laser to obtain two rows of holes, which supply a passageway for analyte vapor during extraction and desorption. The sorbent was prepared by a traditional sol–gel method with both poly(ethylene glycol) and hydroxy‐terminated silicone oil as coating ingredients. Eight polycyclic aromatic hydrocarbons and six benzene series compounds were used as illustrative semi‐volatile and volatile organic compounds in sequence to verify the extraction performance of this porous headspace solid‐phase microextraction probe. It was found that the analysis method combining a headspace solid‐phase microextraction probe and gas chromatography with mass spectrometry yielded determination coefficients of no less than 0.985 and relative standard deviations of 4.3–12.4%. The porous headspace solid‐phase microextraction probe showed no decrease of extraction ability after 200 uses. These results demonstrate that the packed extraction probe with porous structure can be used for headspace solid‐phase microextraction. This novel design may overcome both the stripping and breakage problems of the conventional coating fiber.     

A sol‐gel based solid phase microextraction fiber for the analysis of aliphatic alcohols in apple juices

A new fiber based on titania‐chitin sol‐gel coated on a silver wire for the headspace solid phase microextraction of aliphatic alcohols from apple juice samples was developed. The influences of fiber coating composition and microextraction conditions (extraction temperature, extraction time, and ionic strength of the sample matrix) on the fiber performance were investigated. Also, the influence of temperature and time on desorption of analytes from fiber were studied. Under the optimized conditions, a porous fiber with a high extraction capacity and good thermal stability (up to 250°C) was obtained. The proposed headspace solid‐phase microextraction‐GC method was successfully used for the analysis of aliphatic alcohols in apple juice and concentrate samples. The recovery values were from 92.8 to 98.6%. The RSD (n=5) for all analytes were below 7.8%.     

Polyurethane/polystyrene‐silica electrospun nanofibrous composite for the headspace solid‐phase microextraction of chlorophenols coupled with gas chromatography

A novel electrospun composite nanofiber‐based adsorbent (polyurethane/polystyrene‐silica) was fabricated, characterized, and used in the headspace solid‐phase microextraction of the acetylated derivatives of chlorophenols in water samples before gas chromatography with micro electron capture detection. The surface morphology, chemical composition, thermal stability, and structure of the fibers were investigated by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and Brunauer–Emmett–Teller and Barrett–Joyner–Halenda techniques. The effect of the main parameters influencing the efficiency of the method including extraction temperature, salt concentration, and extraction time was investigated and the optimized conditions were obtained. The linear dynamic ranges were 0.1–800 ng/mL. The relative standard deviations (n = 3) and the limits of detection were 2.64–9.57% and 0.0234–0.830 ng/mL, respectively. The relative recoveries for real samples (river water and sewage of our university campus) were between 90.8 and 111%.     

Investigation of fragrance stability used in the formulation of cosmetic and hygienic products using headspace solid‐phase microextraction by nanostructured materials followed by gas chromatography with mass spectrometry

A new composite coating of polypyrrole and sodium lauryl ether sulfate was electrochemically prepared on a stainless‐steel wire using cyclic voltammetry. The application and performance of the fiber was evaluated for the headspace solid‐phase microextraction of a fragrance in aqueous bleach samples followed by gas chromatography combined with mass spectrometry to assess the fragrance stability in this kind of household cleaning product. To obtain a stable and efficient composite coating, parameters related to the coating process such as scan rate and numbers of cycles were optimized using a central composite design. In addition, the effects of various parameters on the extraction efficiency of the headspace solid‐phase microextraction process such as extraction temperature and time, ionic strength, sample volume, and stirring rate were investigated by experimental design methods using Plackett–Burman and Doehlert designs. The optimum values of 53°C and 28 min for sample temperature and time, respectively, were found through response surface methodology. Results show that the combination of polypyrrole and sodium lauryl ether sulfate in a composite form presents desirable opportunities to produce new materials to study fragrance stability by headspace solid‐phase microextraction.     

Ultrapreconcentration and determination of organophosphorus pesticides in water by solid‐phase extraction combined with dispersive liquid–liquid microextraction and high‐performance liquid chromatography

Solid‐phase extraction coupled with dispersive liquid–liquid microextraction was developed as an ultra‐preconcentration method for the determination of four organophosphorus pesticides (isocarbophos, parathion‐methyl, triazophos and fenitrothion) in water samples. The analytes considered in this study were rapidly extracted and concentrated from large volumes of aqueous solutions (100 mL) by solid‐phase extraction coupled with dispersive liquid–liquid microextraction and then analyzed using high performance liquid chromatography. Experimental variables including type and volume of elution solvent, volume and flow rate of sample solution, salt concentration, type and volume of extraction solvent and sample solution pH were investigated for the solid‐phase extraction coupled with dispersive liquid–liquid microextraction with these analytes, and the best results were obtained using methanol as eluent and ethylene chloride as extraction solvent. Under the optimal conditions, an exhaustive extraction for four analytes (recoveries >86.9%) and high enrichment factors were attained. The limits of detection were between 0.021 and 0.15 μg/L. The relative standard deviations for 0.5 μg/L of the pesticides in water were in the range of 1.9–6.8% (n = 5). The proposed strategy offered the advantages of simple operation, high enrichment factor and sensitivity and was successfully applied to the determination of four organophosphorus pesticides in water samples.     

Modified headspace solid‐phase microextraction for the determination of quantitative relationships between components of mixtures consisting of alcohols,esters, and ethers — impact of the vapor pressure difference of the compounds

The quantitative relationship between analytes established by the headspace solid‐phase microextraction procedure for multicomponent mixtures depends not only on the character and strength of interactions of individual components with solid‐phase microextraction fiber but also on their vapor pressure in the applied headspace solid‐phase microextraction system. This study proves that vapor pressure is of minor importance when the sample is dissolved/suspended in a low‐volatility liquid of the same physicochemical character as that of the used solid phase microextraction fiber coating. It is demonstrated for mixtures of alcohols, esters, ethers and their selected representatives by applying a headspace solid‐phase microextraction system composed of Carbowax fiber and sample solutions in polyethyleneglycol. The observed differences in quantitative relations between components of the examined mixtures established by their direct analysis and by modified headspace solid‐phase microextraction are insignificant (F _exp < F _crit). It is explained by a significant diminution in vapor pressure difference between individual components of the examined mixture in the applied headspace solid phase microextraction system due to low components concentration in polyethyleneglycol suspensions (Raoult's law) and due to strong specific interactions of analyte molecules with polyethyleneglycol molecules.