Multiple Headspace Extraction Research Articles

Human Blood and Plasma Partition Coefficients for C4-C8 n-alkanes, Isoalkanes, and 1-alkenes

Human blood:air and plasma:air partition coefficients for C(4)-C(8) n-alkanes, isoalkanes, and 1-alkenes were determined using multiple headspace extraction coupled with solid phase microextraction and gas chromatography. Mean blood:air partition coefficients expressed in the form of dimensionless blood-to-air concentration ratio (g/mL(b)/g/mL(a)) were 0.183, 0.416, 1.08, 2.71, and 5.77 for C(4)-C(8) n-alkanes; 0.079, 0.184, 0.473, 1.3, and 3.18 for C(4)-C(8) isoalkanes; and 0.304, 0.589, 1.32, 3.5, and 7.01 for C(4)-C(8) 1-alkenes, respectively (n = 8). The reported partition coefficient values increased exponentially with boiling points, molecular weights, and the carbon atoms in the particle. The solubility of 1-alkenes in blood was higher than in plasma, whereas the blood:air and plasma:air partition coefficients of n-alkanes and isoalkanes did not differ significantly. Consequently, additional interactions of 1-alkenes with whole blood seem to occur. The presented findings are expected to be particularly useful for assessing the uptake, distribution, and elimination of hydrocarbons in human organism.

A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment

This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization.

Measurement of isoprene solubility in water, human blood and plasma by multiple headspace extraction gas chromatography coupled with solid phase microextraction

The aim of this study was to determine the solubility (liquid-to-air ratios) of isoprene in water, human blood and plasma. To this end, an experimental setup combining multiple headspace extraction, solid phase microextraction and gas chromatography–mass spectrometry was applied. The water:air partition coefficients of isoprene were determined for the temperature range 4.5–37 °C and amounted to 1.171–0.277 (g mLl−1) (g mLa−1)−1. On the basis of these data, the enthalpy of volatilization was calculated as 29.46 ± 2.83 kJ mol−1. The blood:air partition coefficients at 37 °C were determined for ten normal healthy volunteers spread around a median value of 0.95 ± 0.09 (g mLl−1) (g mLa−1)−1 and were approximately 16% lower than the plasma:air partition coefficients (1.11 ± 0.2). The applied methodology can be particularly attractive for solubility studies targeting species at very low concentrations in the solution, i.e. when headspace sample enrichment is necessary to provide sufficient measurement sensitivity and reliability. This can be especially helpful if environmental or physiological solute levels have to be considered.

Inclusion interactions of cyclodextrins and crosslinked cyclodextrin polymers with linalool and camphor in Lavandula angustifolia essential oil

In the present study, we investigated the feasibility of preparation of novel controlled release systems for the delivery of essential oil used as ambient odors. The inclusion interactions of cyclodextrins (CDs) and β-cyclodextrin polymers with linalool and camphor in Lavandula angustifolia essential oil were investigated by static headspace gas chromatography (SH-GC). The stability constants with monomeric CD derivatives were determined for standard compounds and for the compounds in essential oil. All studied CDs and CD polymers reduce the volatility of the aroma compounds and stable 1:1 inclusion complexes are formed. The retention capacity of the CD derivatives was measured in static experiments. The feasibility of preparation of novel controlled release systems for the delivery of fragrances was investigated by multiple headspace extraction (MHE) experiments.

Analysis of volatile compounds produced by different species of lactobacilli in rye sourdough using multiple headspace extraction

SummaryProfiles of volatile organic compound (VOC) produced by nine individual lactic acid bacteria (LAB) during rye sourdough fermentation were compared by automated SPME and GC/MS‐Tof. The dough samples were inoculated with individual strains, placed inside the headspace vials and incubated during next 24 h. The production or loss of VOC‐s was followed by adsorbing volatiles onto 85‐m Car/PDMS fibre in every 4 h. Volatile profiles differed among LAB species and divided LAB into two main groups – hetero‐ and homofermentative. Hetrofermentative LAB (Lactobacillus brevis; Leuconostoc citreum; Lactobacillus vaginalis, Lactobacillus panis) showed high production of acetic acid, CO2, ethanol, ethylacetate, producing also hexyl acetate, ethyl hexanoate and isopentyl acetate. Whereas homofermentative LAB species (Lactobacillus helveticus; Lactobacillus casei; Lactobacillus sakei; Lactobacillus curvatus) produced a considerable amount of 2,3‐butanedione. Production of l‐leucine methyl ester was unique for Lb. sakei, Lb. casei and Lb. curvatus strains. Lb. helveticus was the only LAB that produced benzaldehyde.

Determination of Inorganic Salt Solubility at a Temperature above the Boiling Point of Water by Multiple Headspace Extraction Gas Chromatography

This paper describes a novel method for the determination of the solubility of sodium carbonate and sodium sulfate in single- and bisalt aqueous solutions at 110 °C, using multiple headspace extraction gas chromatography (MHE-GC). Both benzene alcohol and methanol were used as the tracer compounds whose vapor–liquid equilibrium (VLE) partition coefficients (CV/CL) are related to the concentration of salt in the studied solution, thereby indirectly providing solubility data. During the MHE process, small amounts of water are removed stepwise by a series of headspace vapor extractions, which simulates the evaporation process, resulting in an increase in the salt concentration in the solution and a decrease in the amount of tracer in the headspace vapor. Eventually, the salt concentration reaches saturation (the limit of solubility), a transition point that can be identified experimentally via GC, because of the different behaviors of the tracer loss before and after the salt saturation point. Knowing the salt concentration in the initial solution and gathering data on the amount of water lost in reaching the transition point, we calculated the solubilities of sodium sulfate and sodium carbonate at 110 °C as 30.6 and 31.9 wt %, respectively, which are in good agreement with data reported previously, using more-complex conventional methods. The method reported here has several advantages, including its simplicity and ease of automation.

Quantitative analysis of volatiles from solid matrices of vegetable origin by high concentration capacity headspace techniques: Determination of furan in roasted coffee

The study compares standard addition (SA), stable isotope dilution assay (SIDA) and multiple headspace extraction (MHE) as methods to quantify furan and 2-methyl-furan in roasted coffee with HS-SPME-GC-MS, using CAR-PDMS as fibre coating, d 4-furan as internal standard and in-fibre internal standardization with n-undecane to check the fibre reliability. The results on about 150 samples calculated with the three quantitation approaches were all very satisfactory, with coefficient of variation (CV) versus the U.S. Food and Drug Administration (FDA) method, taken as reference, almost always below the arbitrarily-fixed limit of 15%. Furan was detected in the 1–5 ppm range, 2-methyl-furan in the 4–20 ppm range. Moreover, experimental exponential slopes ( Q) and linearity ( r) of both furan and 2-methyl-furan MHE regression equation on 50 samples were very similar thus making possible to use the same average Q value for all samples of the investigated set and their quantitation with a single determination. This makes this approach very rapid and competitive in-time with SA and SIDA. A non-separative method (HS-SPME-MS) was also developed in view of possible application on-line monitoring of furan and 2-methyl-furan in a pilot-plant with the aim of optimizing the roasting process to reduce these compounds to a minimum. Sampling times of 20 and 5 min were tested, the latter enabling total analysis time to be reduced to about 9 min. The results on 105 samples with both SIDA and MHE approaches were again highly satisfactory most of the samples giving a CV% versus the conventional methods below 20%. In this case too average Q values for both furan and 2-methyl-furan were used for MHE. The separative method presented very good repeatability (RSD% always below 10%) and intermediate precision over three months (RSD% always below 15%); performance were similar for the non-separative method, with repeatability (RSD%) always below 12% and intermediate precision over three months (RSD%) always below 15%. The sensitivity of both separative and non-separative methods was also very good, LOD and LOQ being in the ppb range for both furan and 2-methyl-furan, i.e. well below the amounts present in the roasted coffee samples.

Multiple headspace single-drop micro-extraction for quantitative determination of lactide in thermally-oxidized polylactide

Single-drop micro-extraction (SDME), an emerging micro-extraction technique, was combined with multiple headspace (MHS) extraction to allow quantitative determination of lactide in thermally-oxidized polylactide. Different solvents, drop sizes and extraction times were tested to obtain best extraction efficiency and the method was further developed to obtain a linear regression plot for the multiple extractions. The combination of SDME and MHS extraction offered several advantages over traditional liquid–solid and headspace extraction techniques. No concentration step was needed and loss of volatiles was prevented as the ageing and extraction were performed in a closed system. Matrix effects, that disturb the quantitation of analytes in solid samples, were removed by the multiple headspace extraction.

In Situ Determination of Bacterial Growth by Multiple Headspace Extraction Gas Chromatography

This paper demonstrated an in situ headspace gas chromatography (GC) technique for monitoring bacterial growth using a commercial GC system with a multiple headspace extraction (sampling) mode. The technique was based on measuring the carbon dioxide mass in the headspace of a closed sample vial during the bacteria growth. A mathematic equation was derived in order to calculate the integrated amount of carbon dioxide produced by bacterial growth during the incubation. The method can be used to monitor the bacterial growth rate in a given cultural medium. The present method is very simple, sensitive, and safe.

Static headspace--gas chromatography: theory and practice

Static headspace--gas chromatography: theory and practice

Vapor−Liquid Equilibrium of Binary Mixtures. 2. Ethanol + 2,2,4-Trimethylpentane, 1-Butanol + 2,2,4-Trimethylpentane, and Ethanol + o-Xylene

The activity coefficients of the binary mixtures ethanol + 2,2,4-trimethylpentane, 1-butanol + 2,2,4-trimethylpentane, and ethanol + o-xylene were determined at temperatures of (308.15, 313.15, and 318.15) K. The determination of the vapor phase composition at equilibrium was carried out using headspace gas chromatography analysis. Multiple headspace extraction was used to calibrate the headspace gas chromatograph. Comparison of the experimental phase diagrams with phase diagrams from the literature shows good agreement. The composition of the azeotropes are reported, where they exist. The molar Gibbs energy of mixing is reported for all mixtures studied. The infinite dilution activity coefficients are reported for all components of all mixtures. Some thermodynamic models (those of Wilson, NRTL, UNIQUAC, and Flory−Scatchard) have been compared with regard to their suitability for modeling the experimental data.

Vapor−Liquid Equilibrium of Binary Mixtures. 1. Ethanol + 1-Butanol, Ethanol + Octane, 1-Butanol + Octane

The activity coefficients of the binary mixtures ethanol + 1-butanol, ethanol + octane, and 1-butanol + octane were determined at temperatures of (308.15, 313.15, and 318.15) K. The determination of the vapor phase composition at equilibrium was carried out using headspace gas chromatography analysis. Multiple headspace extraction was used to calibrate the headspace gas chromatograph. Comparison of the phase diagrams produced using standard Legendre orthogonal polynomial techniques with phase diagrams from the literature showed good agreement. The composition of the azeotropes were reported, where applicable.

Rapid Method for Quantitative Analysis of the Aroma Impact Compound, 2-Acetyl-1-pyrroline, in Fragrant Rice Using Automated Headspace Gas Chromatography

A rapid method employing static headspace gas chromatography (HS-GC) has been developed and validated for quantitative analysis of the impact aroma compound, 2-acetyl-1-pyrroline (2AP), in grains of fragrant rice. This developed method excludes wet extraction, and the rice headspace volatiles are brought directly and automatically to GC analysis. The conditions of the static HS autosampler were optimized to achieve high recovery and sensitivity. The most effective amount of rice sample used was 1 g, which provided 51% recovery and a linear multiple headspace extraction (MHE) plot of the peak area of 2AP. The sensitivity of the method was enhanced by utilizing a megabore fused silica capillary column in conjunction with a nitrogen-phosphorus detector (NPD). Method validations performed for both static HS-GC-FID and HS-GC-NPD demonstrated linear calibration ranges of 20-10 000 (r(2) = 0.9997) and 5-8000 (r(2) = 0.9998) ng of 2AP/g of rice sample, respectively. The limits of detection for both systems were 20 and 5 ng of 2AP, and the limits of quantitation were 0.30 and 0.01 g of brown rice sample, respectively. Reproducibility calculated as intraday and interday coefficients of variation were 3.25% RSD (n = 15) and 3.92% RSD (n = 35), respectively, for SHS-GC-FID and 1.87% RSD (n = 15) and 2.85% RSD (n = 35), respectively, for SHS-GC-NPD. The method was found to be effective when applied to the evaluation of aroma quality, based on 2AP concentrations, of some fragrant rice samples.

Novel headspace gas chromatographic method for determination of oxalate in oxygen delignification liquor

A novel headspace gas chromatographic (HS-GC) method is demonstrated for an indirect determination of oxalate in oxygen delignification liquors. A small volume (50–100 μL) of liquor sample is introduced into a sampling vial that contains 1.0 mL of 2 mol/L sulfuric acid. After removal of carbon dioxide (generated from carbonate in the acidic medium) by heating, the sample was mixed with a 0.5 mL of 0.02 mol/L potassium permanganate solution in a closed testing vial. At an elevated temperature (70 °C), the oxalate in the sample is rapidly converted to carbon dioxide by reacting with permanganate. The carbon dioxide in the headspace can be measured by gas chromatography with a thermal conductive detector. Using a multiple headspace extraction (MHE) measurement technique, the kinetics of formation of the carbon dioxide from the other organic species in the sample can be determined, and thus a correction can be made for minimizing the interferences. The present method is simple, accurate and can be easily automated.

Multiple headspace single-drop microextraction—a new technique for quantitative determination of styrene in polystyrene

Single-drop microextraction (SDME), an emerging miniaturised extraction technique, was for the first time combined with multiple headspace extraction (MHE) to enable the quantitative determination of volatiles in solid matrixes by SDME technique. The concept of multiple headspace single-drop microextraction (MHS-SDME) was then applied for quantitative determination of styrene in polystyrene (PS) samples. Good linearity for the multiple headspace extraction was obtained when the migration of styrene was facilitated by grinding the samples and incubating them for 1 h at 150 °C prior the first extraction. Two microlitres of butyl acetate was used as the single-drop microextraction solvent and the extraction time was 5 min per cycle. The relative standard deviation (RSD) for single-drop microextraction of styrene standard at n = 6 was 7.6%. Linearity was shown for styrene concentrations between 0.005 and 0.75 μg/ml ( R 2 = 0.999). This corresponds to total amount of styrene between 0.1 and 15 μg. The limit of quantitation for styrene standard at S/N 10 was 0.005 μg/ml. The developed method was validated against and showed good agreement with an earlier reported dissolution–precipitation method.

Determination of the solubility of a monomer in water by multiple headspace extraction gas chromatography

AbstractIn water‐based polymerization (suspension, microsuspension, emulsion, miniemulsion, and microemulsion polymerization), the solubility of the monomer in the aqueous phase can have profound effects on the final polymer product. This article demonstrates a novel method for the determination of monomer solubility in water with headspace gas chromatography (GC). In this method, an excess amount of an organic solute of interest was added into a closed headspace vial containing a given volume of water. The organic solute and water in the vial was well mixed by strong hand shaking; then, the equilibrated vapor solute in the vial at a desired temperature was measured by headspace GC with a multiple headspace extraction mode. In each headspace extraction, a part of the vapor phase in the vial was vented for GC analysis and replaced with an inert gas. The excess amount of solute in aqueous solution was eventually removed from the vial after multiple headspace extractions, and the solute concentration in water reached its saturation point. After that point, the concentration of the solute in the vapor dramatically decreased in each subsequent headspace extraction. By plotting vapor concentration versus headspace extraction number, we determined the transition point. The vapor concentration at this point corresponded to the solute solubility, which was calculated through a calibration. This method was very simple and automated; it could easily be used for organic solute solubility measurement at an elevated temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1296–1301, 2006

Automated Multiple Headspace Extraction Procedure: Adsorption Modeling and Determination of Air-to-Water Partition Coefficients

The present work makes the first attempt to take into account adsorptions in the determination of partition coefficients by modeling the multiple headspace extraction (MHE) process. Modeling a six-step MHE procedure of a homologous series of methyl ketones revealed that their adsorption-desorption on the walls was the rate-limiting step. Moreover, a comparison between experimental and predicted MHE plots shows that only the last MHE points were affected by adsorption phenomena. Using cell materials with the lowest sorptive properties, partition coefficients were then accurately calculated from the first four MHE steps. This kinetic approach supports previous work in which adsorptions were lowered owing to the choice of sampling cell materials. It also justifies some reproducibility limitations of the MHE quantification procedure mentioned in the literature.

Determination of Air-To-Water Partition Coefficients Using Automated Multiple Headspace Extractions

Air-to-water partition coefficients are experimentally determined using a multiple headspace extraction procedure and an automated headspace cell. The approach is first validated with 2-butanone and then applied to a homologous series of methyl ketones. As adsorptions of the most hydrophobic compounds occurred in the sampling cell, technical improvements have been tested. This study represents the first attempt to overcome analyte adsorptions by studying and minimizing the effect of the cell's adsorption of hydrophobic analytes on the determination of their partition coefficients. The present method allows the measurement of several analytes at the same time, in the ppm range, without calibration, and with a limited manpower.

Simplified multiple headspace extraction gas chromatographic technique for determination of monomer solubility in water

This paper reports an improved headspace gas chromatographic (GC) technique for determination of monomer solubilities in water. The method is based on a multiple headspace extraction GC technique developed previously [X.S. Chai, Q.X. Hou, F.J. Schork, J. Appl. Polym. Sci., in press], but with the major modification in the method calibration technique. As a result, only a few iterations of headspace extraction and GC measurement are required, which avoids the “exhaustive” headspace extraction, and thus the experimental time for each analysis. For highly insoluble monomers, effort must be made to minimize adsorption in the headspace sampling channel, transportation conduit and capillary column by using higher operating temperature and a short capillary column in the headspace sampler and GC system. For highly water soluble monomers, a new calibration method is proposed. The combinations of these technique modifications results in a method that is simple, rapid and automated. While the current focus of the authors is on the determination of monomer solubility in aqueous solutions, the method should be applicable to determination of solubility of any organic in water.

Measurement of the Solubilities of Vinylic Monomers in Water

In aqueous emulsion and miniemulsion polymerization, the product may be dependent upon the ability of the monomer(s) to diffuse across the continuous aqueous phase. This, in turn, is dependent upon the solubility of the monomer in the aqueous phase. Reference solubilities are often difficult to find or measure using different methods and temperatures. This paper presents the solubilities of a number of low-solubility monomers at 60 °C, using the multiple headspace extraction gas chromatography technique described by Chai et al. (J. Appl. Polym. Sci. 2004, in press). The data were collected under uniform conditions and provide a base for judging relative solubilities. These data will be useful not only as absolute measurements of water solubility but also as a tool to judge the relative solubilities of various monomers.