Comparison of static headspace, headspace solid phase microextraction, headspace sorptive extraction, and direct thermal desorption techniques on chemical composition of French olive oils

Static headspace (SHS), headspace solid phase microextraction (HS-SPME), headspace sorptive extraction (HSSE), and direct thermal desorption (DTD) were applied to the analysis of four French virgin olive oils from Corsica. More than 60 compounds were isolated and characterized by GC-RI and GC-MS. SHS was not suited to the characterization of olive oil volatile compounds because of low sensitivity. The SPME and HSSE techniques were successfully applied to olive oil headspace analysis. Both methods allow the characterization of volatile compounds (mainly C(6) aldehydes and alcohols), which contribute significantly to the "green" flavor note of virgin olive oils. The PDMS stir bar showed a higher concentration capacity than a DVB/CAR/PDMS SPME fiber due to the higher volume of polymeric coating. DTD was a very good tool for extracting volatile and especially semivolatile compounds, such as sesquiterpenes, but requires a significant investment like that for HSSE. Finally, SPME may be a more appropriate technique for routine quality control due to its operational simplicity, repeatability, and low cost.     

Solid phase microextraction (SPME) of orange juice flavor: odor representativeness by direct gas chromatography olfactometry (D-GC-O)

The sensorial quality of solid phase microextraction (SPME) flavor extracts from orange juice was measured by direct gas chromatogrphy-olfactometry (D-GC-O), a novel instrumental tool for evaluating odors from headspace extracts. In general, odor impressions emerging from SPME extracts poorly resembled that of the original orange juice. In an attempt to improve the sensorial quality of extracts, sample equilibration and exposure times were varied on Carboxen/polydimethylsiloxane (CAR/PDMS) and divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) SPME fibers. Best sensorial results were obtained with the DVB/CAR/PDMS fiber exposed for the shortest time; a trained panel of eight assessors judged its odor as the most representative of the reference orange juice. The analysis of odor active compounds by classical GC-O accounted for odor characteristics revealed by D-GC-O. A principal component analysis (PCA) was applied on SPME and headspace extracts using flavor recoveries as variables. Interestingly, PCA discriminated samples according to their odor representations described by D-GC-O analysis. This paper provides the first comprehensive methodology to "smell" SPME extracts and "evaluate" their sensorial quality. This method will enable future investigations to further improve SPME performance.     

Effects of an Industrial Milling Process on Change of Headspace Volatiles in Yihchuan Aromatic Rice

Headspace volatiles of Yihchuan aromatic rice, a japonica rice cultivar, were extracted by a solid‐phase microextraction (SPME) method and analyzed by GC and GC‐MS. Effects of fiber types and an industrial milling process on the change of headspace volatiles were studied. Of the fiber types, divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), and carboxen/polydimethylsiloxane (CAR/PDMS) were suggested for use in the analysis headspace volatiles in terms of absorption or adsorption ability. Regarding the milling effect, the amount of total headspace volatiles from brown rice to white rice decreased ≈30%, and that of aldehydes and alcohols, the two largest groups of volatiles, decreased ≈20 and 15%, respectively. Comparatively, rice bran contained higher amounts of total headspace volatiles than milled rice grains.     

Analysis of 2‐Acetyl‐1‐Pyrroline in Rice by HSSE/GC/MS

An extremely sensitive method for the analysis of 2‐acetyl‐1‐pyrroline (2AP) in rice, employing stir bar sorptive extraction (Twister) was studied. The Twister stir bar is placed in the headspace of a 20‐mL vial containing 1 g of rice kernels, 7.5 mL of 0.1M KOH, and 2.2 g of NaCl, along with a second Teflon‐coated stir bar for mixing. Analytes are adsorbed onto the Twister for 4 hr at 40°C and then desorbed at 270°C into a GC column while cryofocusing at –80°C. The headspace sorptive extraction (HSSE) method was able to detect <0.1 ppb of 2AP in rice. The precision of the HSSE method (>10%) was not as good as the GC/FID method (≈6%). Using HSSE, 2AP was observed in all samples generally considered to be aromatic and was not observed in any nonaromatic samples. Additionally, a modified method for the synthesis of 2‐acetyl‐1‐pyrroline was studied and the presence of a tautomer of 2‐acetyl‐1‐pyrroline was confirmed.     

Analysis of volatiles in Pinotage wines by stir bar sorptive extraction and chemometric profiling

A fast, simple, cost-effective, and reliable method based on stir bar sorptive extraction (SBSE) in the headspace mode was used for the analysis of 39 volatile components in Pinotage wines. The method was sensitive, with LODs ranging from 50.0 pg/L to 281 ng/L and LOQs between 180 pg/L and 938 ng/L. Precision was between 6 and 20%. The intermediate precision was within the acceptable range. Moreover, good calibration curves with R(2) > 0.99 for all compounds were achieved. The method was successfully applied for the analysis of 87 young Pinotage wines of vintages 2005 and 2006 collected from various South African regions. To characterize the results based on vintage and origin, the obtained concentrations of the compounds were subjected to chemometric analysis. Exploratory factor analysis (FA), principal component analysis (PCA), and analysis of variance (one-way ANOVA) were consecutively done. The chemometrics approach revealed a reasonable correlation among the volatile components of these wines, as well as with respect to their year of production.     

Microwave-assisted headspace solid-phase microextraction for the analysis of bioemissions from Eucalyptus citriodora leaves

Microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) was developed as a simple and effective method for fast sampling of volatile organic compounds (VOCs) from Eucalyptus citriodora Hook (E. citriodora) leaves. During microwave heating, a simple shielding device made of aluminum foil was used to protect the SPME fiber from microwave irradiation while allowing the sample to be heated. A room temperature water bath was also used to allow microwave heating to be conducted in a more controlled manner. The inner heating caused by microwave irradiation dramatically accelerated the emission of VOCs from the sample, but no marked change in headspace temperature in the sample vial was found. Under optimum conditions, the extraction efficiencies obtained with microwave heating were much higher than those obtained without microwave heating for all fibers used, namely, 7-microm polydimethylsiloxane (PDMS), 100-microm polydimethylsiloxane (PDMS), 65-microm polydimethylsiloxane/divinylbenzene (PDMS/DVB), and 75-microm carboxen/polydimethylsiloxane (CAR/PDMS). The improvement of extraction efficiency using MA-HS-SPME allowed more VOC events to be detected, with more balanced extraction of VOCs of lower and higher molecular masses. Moreover, a good linear relationship was found between sample size and GC-FID response (total peak area of VOCs), indicating the usefulness of MA-HS-SPME for quantitative analysis of individual volatile compounds in E. citriodora leaves.     

Stir bar sorptive extraction applied to volatile constituents evolution during Vitis vinifera ripening

The stir bar sorptive extraction (SBSE) technique is used to determine volatile constituents in Monastrell grapes. The method proposed involves a maceration step lasting 2 h and a sorption time of 6 h. The coefficients of variation obtained were <4% in the case of the volatile compounds and <2% for the internal standard. The behavior of the volatiles during grape ripening was studied, and 34 compounds were determined, among which geranyl acetone, geranyl butyrate, farnesol, and a bicycloterpene, tentatively identified as 6-methylene[3.1.0]byciclohexane, were recorded for the first time in this variety. The highest terpene and norisoprenoid contents together with the lowest values of C6 compounds were observed during the fifth week of ripening, meaning that this would be the optimal time for harvesting in terms of volatile compounds.     

Solid-phase microextraction method development for headspace analysis of volatile flavor compounds

Solid-phase microextraction (SPME) fibers were evaluated for their ability to adsorb volatile flavor compounds under various conditions with coffee and aqueous flavored solutions. Experiments comparing different fibers showed that poly(dimethylsiloxane)/divinylbenzene had the highest overall sensitivity. Carboxen/poly(dimethylsiloxane) was the most sensitive to small molecules and acids. As the concentrations of compounds increased, the quantitative linear range was exceeded as shown by competition effects with 2-isobutyl-3-methoxypyrazine at concentrations above 1 ppm. A method based on a short-time sampling of the headspace (1 min) was shown to better represent the equilibrium headspace concentration. Analysis of coffee brew with a 1-min headspace adsorption time was verified to be within the linear range for most compounds and thus appropriate for relative headspace quantification. Absolute quantification of volatiles, using isotope dilution assays (IDA), is not subject to biases caused by excess compound concentrations or complex matrices. The degradation of coffee aroma volatiles during storage was followed by relative headspace measurements and absolute quantifications. Both methods gave similar values for 3-methylbutanal, 4-ethylguaiacol, and 2,3-pentanedione. Acetic acid, however, gave higher values during storage upon relative headspace measurements due to concurrent pH decreases that were not seen with IDA.     

Application of a headspace sorptive extraction method for the analysis of volatile components in South African wines

A headspace sorptive extraction (HSSE) in combination with thermal desorption gas chromatography-mass spectrometry (TD-GC-MS) method for the analysis of volatile components (alcohols, esters, carbonyls, acids, phenols and lactones) in wine samples was developed. Extraction conditions such as salting-out effects, sorption time, stirring speed, phase ratio, extraction temperature, and effect of pH were thoroughly evaluated as part of method validation. The method was very sensitive with LODs and LOQs between 50 pg/L to 299 microg/L and 0.2 ng/L to 0.996 microg/L, respectively. Repeatability for all the compounds was between 3 and 22%. The intermediate repeatability was obtained within the acceptable range. Out of 39 volatile compounds selected, 37 were detected and quantitated. The method was found to be simple, cost-effective, sensitive, and use a small sample volume. The method was successfully applied for the routine analysis of 79 young red and white wine samples from various South African districts.     

SPME applied to the study of volatile organic compounds emitted by three species of Eucalyptus in situ. Solid-phase micro extraction

Headspace solid-phase microextraction coupled to gas chromatography/ion trap mass spectrometry-65 microm polydimethylsiloxane/divinylbenzene (PDMS/DVB) was used to identify and monitor the emission patterns of biogenic volatile organic compounds from leaves of Eucalyptus dunnii, Eucalyptus saligna, and Eucalyptus citriodora in situ. Short extractions (1 min) were performed every 30 min for periods of 8-10 h during 24 days taking advantage of the high capacity of this porous polymer coating. Forty-two compounds were detected and 20 identified in the headspace of E. saligna leaves, and 19 of 27 compounds were identified in the headspace of E. dunnii leaves. The emission pattern of (E)-beta-ocimene and rose oxide suggests that they may play a bioactive role in Eucalyptus.     

Model studies on the influence of coffee melanoidins on flavor volatiles of coffee beverages

Addition of the total melanoidin fraction isolated by water extraction from medium-roasted coffee powder to a model solution containing a set of 25 aroma compounds mimicking the aroma of a coffee brew reduced, in particular, the intensity of the roasty, sulfury aroma quality. Model studies performed by static headspace analysis revealed that especially three well-known coffee odorants, that is, 2-furfurylthiol (FFT), 3-methyl-2-butene-1-thiol, and 3-mercapto-3-methylbutyl formate, were significantly reduced in the headspace above an aqueous model solution when melanoidins were added. In particular, the low molecular weight melanoidins (1500-3000 Da) led to the most significant decrease in FFT. In contrast, for example, aldehydes remained unaffected by melanoidin addition.     

Volatile composition in raspberry cultivars grown in the Pacific Northwest determined by stir bar sorptive extraction-gas chromatography-mass spectrometry

Twenty-nine volatile compounds in 'Chilliwack', 'Tulameen', 'Willamette', 'Yellow Meeker', and 'Meeker' raspberries were quantified using stir bar sorptive extraction (SBSE) paired with gas chromatography-mass spectrometry (GC-MS). Good correlation coefficients were obtained with most aroma-active compounds in raspberry, with quantification limits of 1 microg/kg. However, poor recoveries were observed for raspberry ketone and zingerone. Quantitative data showed that volatile concentrations varied for different cultivars. Large variations for alpha-ionone, beta-ionone, geraniol, linalool, and ( Z)-3-hexenol were observed in different raspberry cultivars. In addition, the volatile compositions in 'Meeker' raspberry grown at different locations also varied. The chiral isomeric ratios of raspberry ketone, alpha-ionone, alpha-pinene, linalool, terpinen-4-ol, delta-octalactone, delta-decalactone, and 6-methyl-5-hepten-2-ol were studied using a CyclosilB column. alpha-Ionone, alpha-pinene, delta-octalactone, and delta-decalactone had strong chiral isomeric preference, with more than 96% for one isomeric form. Much weaker chiral isomeric preference was observed for terpinen-4-ol, while linalool was almost a racemic mixture. Both growing locations and cultivars affect the isomeric ratio of linalool with a range of 37-51% for ( R)-linalool.     

Headspace solid phase microextraction applied to the analysis of organophosphorus insecticides in strawberry and cherry juices

A method based on a headspace solid phase microextraction (HS-SPME) technique followed by gas chromatography with flame thermionic and mass spectrometric detection was developed for the determination of seven organophosphorus (OPs) insecticide residues in strawberry and cherry juice samples. The extraction capacities of four fiber coatings, polyacrylate (PA 85 microm), poly(dimethylsiloxane) (PDMS 100 microm), carbowax-divinylbenzene (CW-DVB 65 microm), and poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB 65 microm), have been studied and compared. The method was developed using spiked strawberry and cherry juices in a concentration range of 0.5-50 microg/L. The PDMS 100 microm fiber showed good extraction efficiency for the target compounds. An increase in the extraction efficiency of OP insecticides was observed when the parameters affecting the HS-SPME process such as temperature, extraction time, salt additives, stirring rate, pH, and effect of dilution were optimized. Good linearity of compounds was observed in the tested concentration range. The relative standard deviations were found to be <20%. The limits of detection were between 0.025 and 0.050 microg/L. The mean relative recoveries ranged from 82 to 102%.     

Analysis of volatile compounds released during the grinding of roasted coffee beans using solid-phase microextraction

A dynamic solid-phase microextraction (SPME) method to sample fresh headspace volatile compounds released during the grinding of roasted coffee beans was described and the analytical results using gas chromatography/mass spectrometry (GC/MS) and GC/olfactometry (GC/O) were compared to those of the conventional static SPME sampling methods using ground coffee. Volatile compounds released during the grinding of roasted coffee beans (150 g) were obtained by exposing the SPME fiber (poly(dimethylsiloxane)/divinylbenzene, PDMS/ DVB) for 8 min to nitrogen gas (600 mL/min) discharged from a glass vessel in which the electronic coffee grinder was enclosed. Identification and characterization of volatile compounds thus obtained were achieved by GC/MS and GC/O. Peak areas of 47 typical coffee volatile compounds, separated on total ion chromatogram (TIC), obtained by the dynamic SPME method, showed coefficients of variation less than 5% (n = 3) and the gas chromatographic profile of volatile compounds thus obtained was similar to that of the solvent extract of ground coffee, except for highly volatile compounds such as 4-hydroxy-2,5-dimethyl-3(2H)-furanone and 4-ethenyl-2-methoxyphenol. Also, SPME dilution analysis of volatile compounds released during the grinding of roasted coffee beans showed linear plots of peak area versus exposed fiber length (R (2) > 0.89). Compared with those of the headspace volatile compounds of ground coffee using GC/MS and GC/O, the volatile compounds generated during the grinding of roasted coffee beans were rich in nutty- and smoke-roast aromas.     

Interactions between volatile and nonvolatile coffee components. 1. Screening of nonvolatile components

This study is the first of two publications that investigate the phenomena of coffee nonvolatiles interacting with coffee volatile compounds. The purpose was to identify which coffee nonvolatile(s) are responsible for the interactions observed between nonvolatile coffee brew constituents and thiols, sulfides, pyrroles, and diketones. The overall interaction of these compounds with coffee brews prepared with green coffee beans roasted at three different roasting levels (light, medium, and dark), purified nonvolatiles, and medium roasted coffee brew fractions (1% solids after 1 or 24 h) was measured using a headspace solid-phase microextraction technique. The dark roasted coffee brew was slightly more reactive toward the selected compounds than the light roasted coffee brew. Selected pure coffee constituents, such as caffeine, trigonelline, arabinogalactans, chlorogenic acid, and caffeic acid, showed few interactions with the coffee volatiles. Upon fractionation of medium roasted coffee brew by solid-phase extraction, dialysis, size exclusion chromatography, or anion exchange chromatography, characterization of each fraction, evaluation of the interactions with the aromas, and correlation between the chemical composition of the fractions and the magnitude of the interactions, the following general conclusions were drawn. (1) Low molecular weight and positively charged melanoidins present significant interactions. (2) Strong correlations were shown between the melanoidin and protein/peptide content, on one hand, and the extent of interactions, on the other hand (R = 0.83-0.98, depending on the volatile compound). (3) Chlorogenic acids and carbohydrates play a secondary role, because only weak correlations with the interactions were found in complex matrixes.     

Biogenetic studies in Syringa vulgaris L.: bioconversion of (18)O(2H)-labeled precursors into lilac aldehydes and lilac alcohols

Syringa vulgaris L. inflorescences, petals, and chloroplasts, isolated from lilac flower petals, were fed with aqueous solutions of (18)O-labeled linalool and [5,5-(2)H(2)]-deoxy-d-xylose (DOX). The chloroplasts of lilac flower petals were isolated after feeding experiments with labeled precursors. Volatiles from the chloroplasts were extracted by stir bar sorptive extraction (SBSE) and analyzed using enantioselective multidimensional gas chromatography-mass spectrometry (enantio-MDGC-MS). Feeding experiments with DOX indicate that the novel mevalonate-independent 1-deoxy-d-xylose 5-phosphate/2C-methyl-d-erythritol 4-phosphate (DOX/MEP) is the decisive pathway of lilac aldehyde and lilac alcohol, respectively. Bioconversion of [(18)O]linalool into lilac aldehyde and lilac alcohol during in vivo feeding experiments was monitored, and the metabolic pathways are discussed.     

Comparison of solid-phase microextraction and stir bar sorptive extraction for the quantification of malodors in wastewater

Malodors in wastewater from animal-rearing facilities are due to the presence of characteristic polar compounds. The efficiency and reproducibility of three solid-phase microextraction (SPME) fibers (Carboxen-PDMS, polyacrylate, and PDMS) as well as PDMS-coated stir bars for the measurement of some of these compounds in the liquid phase were compared. In initial experiments, the SPME fibers and stir bars were exposed to a standard water solution containing a mixture of 18 compounds with a range of octanol-water partition coefficients. The polyacrylate SPME fibers and PDMS-coated stir bars, having been found to possess the best combination of extraction efficiency and reproducibility of measurement, were compared for the extraction of a high-strength swine wastewater. Ten compounds, which are known contributors to malodors in wastewater, were quantified by both methods of extraction. For most compounds, greater levels were estimated by the PDMS-coated stir bars than by SPME, and measurement reproducibility was also greater. For both methods of extraction, there was greater variation in the measurement of volatile fatty acids than there was for aromatics.     

Determination of polycyclic aromatic hydrocarbons in coffee brew using solid-phase extraction

The presence of polycyclic aromatic hydrocarbons (PAHs) in coffee has been reported and is suspected to be due to the degradation of coffee compounds during the roasting step. Due to the high toxicity of these compounds, among which benzo[a]pyrene is known to be the most carcinogenic, their presence in the coffee, especially the coffee brew that is directly ingested by the consumer, is of prime importance. However, due to the low solubility of these compounds, their concentrations are expected to be rather low. As a consequence, reliable and sensitive analytical methods are required. The aim of this study was to develop a reliable and fast analytical procedure to determine these organic micropollutants in coffee brew samples. PAHs were retained on a 0.5 g polystyrene-divinylbenzene cartridge before being eluted by a mixture of methanol/tetrahydrofuran (10:90 v/v), concentrated, and directly analyzed by reversed-phase high-performance liquid chromatography coupled to a fluorescence detector. Application to the determination of PAHs in several coffee brew samples is also given, with mean estimated concentrations in the range of 0-100 ng L(-1) for suspected benzo[b]fluoranthene and benzo[a]pyrene, whereas no fluoranthene could be detected. Tentative identification was made on the basis of UV spectra. However, identification of the suspected traces of PAHs could not be achieved due to matrix effects, so that the presence of coeluting compounds may not be excluded.     

Ochratoxin a determination in beer by solid-phase microextraction coupled to liquid chromatography with fluorescence detection: a fast and sensitive method for assessment of noncompliance to legal limits

A solid-phase microextraction-liquid chromatography-fluorescence detection (SPME-LC-FD) method for the determination of ochratoxin A (OTA) in commercial beer samples was developed for the first time using a 60 microm thick poly(dimethylsiloxane)/divinylbenzene (PDMS/DVB) fiber. The procedure required a very simple sample pretreatment, an isocratic elution, and provides a selective extraction. All of the factors influencing fiber adsorption (extraction time, temperature, pH, and salt addition) and desorption of the analyte (desorption and injection time and desorption solvent mixture composition) have been investigated. The linear range investigated in beer was 0.03-2 ng/mL; within-day and between-days relative standard deviation in beer were 4.3 and 5.9%, respectively. The limit of quantification in spiked beer was 53 pg mL(-)(1), well below all European regulatory levels.     

Low molecular weight melanoidins in coffee brew

Analysis of low molecular weight (LMw) coffee brew melanoidins is challenging due to the presence of many non-melanoidin components that complicate analysis. This study focused on the isolation of LMw coffee brew melanoidins by separation of melanoidins from non-melanoidin components that are present in LMw coffee brew material. LMw coffee fractions differing in polarity were obtained by reversed-phase solid phase extraction and their melanoidin, sugar, nitrogen, caffeine, trigonelline, 5-caffeoylquinic acid, quinic acid, caffeic acid, and phenolic groups contents were determined. The sugar composition, the charge properties, and the absorbance at various wavelengths were investigated as well. The majority of the LMw melanoidins were found to have an apolar character, whereas most non-melanoidins have a polar character. The three isolated melanoidin-rich fractions represented 56% of the LMw coffee melanoidins and were free from non-melanoidin components. Spectroscopic analysis revealed that the melanoidins isolated showed similar features as high molecular weight coffee melanoidins. All three melanoidin fractions contained approximately 3% nitrogen, indicating the presence of incorporated amino acids or proteins. Surprisingly, glucose was the main sugar present in these melanoidins, and it was reasoned that sucrose is the most likely source for this glucose within the melanoidin structure. It was also found that LMw melanoidins exposed a negative charge, and this negative charge was inversely proportional to the apolar character of the melanoidins. Phenolic group levels as high as 47% were found, which could be explained by the incorporation of chlorogenic acids in these melanoidins.