Headspace Gas Chromatography-flame Ionization Detection Research Articles

An analysis method for determining residual hexane in health functional food products using static headspace gas chromatography.

A method for analyzing the contents of residual hexane in health functional food products was developed. The dissolving solvents in the health functional food products and the internal standard selected were N,N-dimethylacetamide and heptane, respectively. The analysis conditions for headspace-gas chromatography/flame ionization detection (HS-GC/FID) and headspace-gas chromatography/mass spectrometry (HS-GC/MS) were determined as 18 mL of headspace volume, 100°C of headspace oven temperature, and 30 min of equilibration time; a Durabond (DB)-624 column was selected for this analysis. To validate this method, which applies N,N-dimethylacetamide as a dissolving solvent, the limit of detection and limit of quantification (LOQ) values based on the HS-GC/FID and HS-GC/MS analyses results were found to be 0.10, 0.29 and 0.16, 0.47 mg/L, respectively. The recoveries and coefficient of variation (CV) obtained by HS-GC/MS were 96.39-119.86% and 0.04-1.25%, respectively, better than those obtained by HS-GC/FID. By applying the HS-GC/MS method, it was possible to analyze the content of the residual hexane in 60 different types of health functional food products.

Assessment of carboxyhemoglobin, hydrogen cyanide and methemoglobin in fire victims: a novel approach

To establish the cause of death, carboxyhemoglobin (COHb), total hemoglobin (tHb), methemoglobin (MetHb), and hydrogen cyanide (HCN) were quantified in the blood of fire victims. We analyzed 32 out of 33 blood samples from forensic autopsy cases in a disastrous polyurethane mattress fire, which caused the deaths of 33 inmates at a prison in Argentina in 2006.The cadaveric blood samples were collected by femoral vein puncture. These samples were analyzed using the IL80 CO-oximeter system for tHb, MetHb, and COHb levels and by microdiffusion for HCN and COHb levels. Blood alcohol (ethanol) and drugs were examined by headspace gas chromatography–flame ionization detection (HS-GC–FID) and GC–mass spectrometry (MS), respectively. Polyurethane mattress samples were analyzed according to the California 117 protocol.The saturation of COHb ranged from 10% to 43%, tHb from 2% to 19.7%, MetHb from 0.10% to 35.7%, and HCN from 0.24 to 15mg/L. These HCN values are higher than the lethal levels reported in the literature. Other toxic components routinely measured (ethanol, methanol, aldehydes, and other volatile compounds) gave negative results in the 32 cases. Neither drugs of abuse nor psychotropic drugs were detected. The results indicate that death in the 32 fire victims was probably caused in part by HCN, generated during the extensive polyurethane decomposition stimulated by a rapid increase in temperature. We also considered the influence of oxygen depletion and the formation of other volatile compounds such as NOx in this disaster, as well as pathological evidence demonstrating that heat was not the cause of death in all victims. Furthermore, statistical analysis showed that the percentage values of COHb and MetHb in the blood were not independent variables, with χ2=11.12 (theoretical χ2=4.09, degrees of freedom=12, and α=0.05). However, no correlation was found between HCN and MetHb in the blood of the victims. This is the first report to assess the relationship between COHb and MetHb in forensic blood samples. We further discuss other factors that could lead to a lethal atmosphere generated by the fire and compare the data from this disaster with that of other published fire episodes.

Ethanol Concentration in Breastmilk After the Consumption of Non-alcoholic Beer

During lactation, the consumption of ethanol is discussed controversially. After women drink alcoholic beverages, ethanol can be found in breastmilk with a time lag. To abstain from ethanol, but not from the taste of alcoholic beverages, in particular, non-alcoholic beer has become popular in recent years. According to regulations in the United States and most European countries, these "alcohol-free" beverages may still contain ethanol up to 1.2% by volume. To determine how much of this ethanol may reach the breastfed child, a drinking experiment with non-alcoholic beer was performed. Fifteen healthy breastfeeding women participated in the study. After at least 5 days of abstinence from ethanol and the donation of a void breastmilk sample, they were asked to drink 1.5 L of non-alcoholic beer within 1 hour. Breastmilk samples were collected using electronic breast pumps immediately after the end of drinking as well as 1 and 3 hours later. The milk was analyzed for ethanol by headspace-gas chromatography-flame ionization detection using a fully validated method. In two women, trace amounts of ethanol (up to 0.0021 g/L) were found in the samples gained immediately after the drinking period. In the other samples ethanol could not be detected (limit of detection=0.0006 g/L). The mother's consumption of non-alcoholic beer is likely innocuous for the breastfed infant.

Development of headspace–gas chromatography–flame ionization detection procedure to determine volatile fatty acids in zoo organic waste leachates

In order to determine volatile fatty acids (short chain monocarboxylic acids with 2 to 6 carbon atoms in a molecule) in leachates formed in organic waste piles a procedure based on static headspace (HS) coupled with gas chromatography (GC) have been proposed and optimized. The conditions of HS extraction and sample introduction into a gas chromatograph as well as of chromatographic separation were considered. Using flame ionization detection LODs were of the order of 0.02-0.37 mg/L. The analyzed leachate collecting on and close to a zoo organic waste pile contained VFAs (Volatile Fatty Acids) at a concentration ranging from 5.5 mg/L to 0.88 g/L and from below LOD to 10.1 mg/L for pool water at some distance from the pile, respectively.

Griseofulvin micronization and dissolution rate improvement by supercritical assisted atomization

Supercritical assisted atomization (SAA) was used to micronize griseofulvin (GF), selected as a model compound, to verify the performance of this innovative process. SAA is based on the solubilization of supercritical carbon dioxide in a liquid solution containing the drug. The ternary mixture is then sprayed through a nozzle and microparticles are formed as a consequence of the enhanced atomization. Precipitation temperature and drug concentration in the liquid solution were studied to evaluate their influence on morphology and size of precipitated particles. A good particle size control was obtained and GF spherical particles with mean diameters ranging from 0.5 to 2.5 microm were produced with a narrow particle size distribution. Processed GF was characterized by high-performance liquid chromatography-UV/vis, headspace-gas chromatography-flame ionization detection, differential scanning calorimetry, BET and X-ray analyses. No drug degradation was observed and a solvent residue (acetone) less than 800 ppm was measured. GF microparticles showed good stability and surface areas ranging from about 4 to 6 m(2) g(-1); moreover, the micronized drug retained the crystalline habit. GF capsules were formulated with starch and used to compare the dissolution rate of SAA-processed and conventional jet-milled drug. A faster dissolution and a better reproducibility of the dissolution profile were observed for SAA-processed GF.

Quantitative Endogenous Formate Analysis in Plasma Using Headspace Gas Chromatography Without a Headspace Analyzer

The objective was to develop a simple routine method for quantitative measurement of endogenous formic acid in plasma and whole blood using headspace gas chromatography-flame ionization detection. (GC-FID). Two-hundred microliters of sample was placed in a 1-mL glass vial. Fifty microliters of aqueous ethanol (10%) was added as an internal standard and a derivatizing agent. Ethylformate formation was enhanced by addition of 200 microL concentrated sulfuric acid as a catalyst. The vials were then sealed immediately and placed in a water bath for 15 min at 60 degrees C. One milliliter of this headspace gas was siphoned using a gas-tight syringe and injected into a GC-FID fitted with a capillary column. Ethanol eluted at approximately 3.0 min, and ethylformate eluted around 4.7 min. The limit of quantitation for ethylformate was 0.026 mmol/L, and the limit of detection was 0.020 mmol/L. Imprecisions for spiked plasma samples at 0.25 and 1 mmol/L were 10% and 9%, respectively and recoveries were at 100% and 108%, respectively. A simple, reliable, and highly specific headspace analysis method for quantifying endogenous formate without the use of a headspace analyzer was developed. This method enables the routine clinical analysis of formate in plasma and whole blood samples.

Investigation of sorbic acid volatile degradation products in pharmaceutical formulations using static headspace gas chromatography

An analytical method that allows simultaneous analysis of sorbic acid and its degradation products was developed using static headspace gas chromatography (HS-GC). AT-Aquawax-DA, the capillary column used, showed good selectivity and separation towards sorbic acid and its degradation products. Sorbic acid degradation was investigated in both acidic and aqueous media at room and elevated temperatures. In total 12 sorbic acid degradation products were found, 8 of which could be characterized. The method was investigated for its accuracy towards estimation of degradation products. Using the HS-GC method different batches of pharmaceutical preparations such as cold cream, cetomacrogol cream and vaseline were investigated for sorbic acid degradation products which were estimated by applying the standard addition method. Acetaldehyde was found to be the major degradation product. The other identified degradation products were: acetone; 2-methylfuran; crotonaldehyde; alfa-angelicalactone; 2-acetyl, 5-methylfuran; toluene and 2,5-dimethylfuran. Both mass spectrometeric (MS) and flame ionization detection (FID) were used. The qualitative investigation was done on HS-GC–MS and the quantitative work on HS-GC–FID.

Ethanol analysis from biological samples by dual rail robotic autosampler

Detection, identification, and quantitation of ethanol and other low molecular weight volatile compounds in liquid matrices by headspace gas chromatography–flame ionization detection (HS–GC–FID) and headspace gas chromatography–mass spectrometry (HS–GC–MS) are becoming commonly used practices in forensic laboratories. Although it is one of the most frequently utilized procedures, sample preparation is usually done manually. Implementing the use of a dual-rail, programmable autosampler can minimize many of the manual steps in sample preparation. The autosampler is configured so that one rail is used for sample preparation and the other rail is used as a traditional autosampler for sample introduction into the gas chromatograph inlet. The sample preparation rail draws up and sequentially adds a saturated sodium chloride solution and internal standard (0.08%, w/v acetonitrile) to a headspace vial containing a biological sample, a calibrator, or a control. Then, the analytical rail moves the sample to the agitator for incubation, followed by sampling of the headspace for analysis. Using DB-624 capillary columns, the method was validated on a GC–FID and confirmed with a GC–MS. The analytes (ethanol, acetonitrile) and possible interferences (acetaldehyde, methanol, pentane, diethyl ether, acetone, isopropanol, methylene chloride, n-propanol, and isovaleraldehyde) were baseline resolved for both the GC–FID and GC–MS methods. This method demonstrated acceptable linearity from 0 to 1500 mg/dL. The lower limit of quantitation (LOQ) was determined to be 17 mg/dL and the limit of detection was 5 mg/dL.

An Automated Alcohol Dehydrogenase Method for Ethanol Quantification in Urine and Whole Blood

In a previous work, an automated alcohol dehydrogenase method for the quantification of ethanol in whole blood (blood) specimens was presented. In the present work the application of the method to urine specimens has been investigated. Also, method robustness to routine analysis of urine and blood specimens during a period of eight months is shown. The limits of detection and quantification for urine were 0.0012 g/dL and 0.0042 g/dL, respectively. Relative standard deviations for the repeatability and within-laboratory reproducibility were in the ranges 1.4-4.1% and 1.8-4.6%, respectively. The method was compared with two headspace gas chromatography-flame ionization detection methods using authentic forensic urine specimens (n = 305) and blood specimens (n = 3186). Passing-Bablok regression for the concentration range 0.01-0.48 g/dL (urine) and 0.002-0.40 g/dL (blood) showed a statistically significant difference, for urine y = 0.9313 (0.9250 - 0.9377)x + 0.0038 (0.0029-0.0044) and for blood y = 0.9493 (0.9491 - 0.9495)x + 0.0032 (0.00318-0.00323), at 95% confidence level. The results of the external quality control specimens were in accordance with the reported theoretical concentrations.

Fast Quantification of Ethanol in Whole Blood Specimens by the Enzymatic Alcohol Dehydrogenase Method. Optimization by Experimental Design

A sensitive, fast, simple, and high-throughput enzymatic method for the quantification of ethanol in whole blood (blood) on Hitachi 917 is presented. Alcohol dehydrogenase (ADH) oxidizes ethanol to acetaldehyde using the coenzyme nicotinamide adenine dinucleotide (NAD), which is concurrently reduced to form NADH. Method development was performed with the aid of factorial design, varying pH, and concentrations of NAD+ and ADH. The linear range increased and reaction end point decreased with increasing NAD+ concentration and pH. The method was linear in the concentration range 0.0024-0.4220 g/dL. The limits of detection and quantification were 0.0007 g/dL and 0.0024 g/dL, respectively. Relative standard deviations for the repeatability and within-laboratory reproducibility were in the ranges 0.7-5.7% and 1.6-8.9%, respectively. The correlation coefficient when compared with headspace gas chromatography-flame ionization detection methods was 0.9903. Analysis of authentic positive blood specimens gave results that were slightly lower than those of the reference method.

Chemical and sensory properties of liquid beet sugar.

Sensory analysis and headspace gas chromatography-flame ionization detection (GC-FID) analysis of liquid sugars (sucrose) designated for food-industrial use were performed in order to elucidate which compounds are responsible for perceived off-odors and off-flavors in liquid sugar. The liquid sugar samples investigated had various kinds of off-odors and off-flavors that might influence the quality of any food product in which they might be used, such as a jam or a soft drink. The sensory scores for the different attributes and the levels of different volatile compounds as measured by GC were analyzed for correlation using partial least-squares (PLS) analysis. A link between sensory analysis and GC analysis was thereby established, and compounds critical for the odor and flavor were identified using MS (mass spectrometry). Approximately 10 compounds were found to be correlated with the defined sensory attributes. Among these compounds associated with the sensory attributes were dimethyl disulfide, 2,6-dimethylpyrazine, 4-methoxyphenol, and 2, 5-dimethylfuran.

Determination of Trace Solvents in Hydraulic Fluid by Equilibrium Headspace Analysis

Equilibrium headspace analysis is applied to the determination of trace solvents in hydraulic fluid. Analysis by headspace gas chromatography—flame ionization detection (GC—FID) showed that 2-propanol, dichloromethane, 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113), n-hexane, 1,2-dichloroethane, and 1,1,1-trichloroethane in hydraulic fluid can be determined with a linear response in the 10–500 ppm range. Headspace analysis avoids the injection of large amounts of low volatility material onto the column, reducing column wear and analysis time.