Simplification of determination method for standard materials using post-column reaction GC/FID

For the simple and fast preparation of highly reliable standard materials, a post-column reaction GC/FID system was developed and evaluated on the mixture of oxygen-containing organic compounds. The oxygen-containing organic compounds mixing solution were determined with the post-column reaction GC/FID system using n-dodecane as an internal calibration standard. Required value of relative expanded uncertainty as an original source of SI-traceable standard materials was within 1% and it aimed at this value as accuracy of the quantitative analysis. The results showed good agreement between the prepared concentrations and analytical values using post-column reaction GC/FID system. These results indicated that the post-column reaction GC/FID system would be used for getting SI-traceable values.     

痕量磷化氢的冷阱二次富集机理与GC/FID分析方法研究

将火焰离子化检测器(FID)应用于二次富集气相色谱检测中构建了冷阱二次富集-GC/FID系统检测环境中痕量磷化氢的分析方法。研究了冷阱温度、载气流量、柱温箱温度和检测器温度对该系统富集检测效果的影响,讨论了磷化氢富集的机理,并将该系统应用于广州地区典型水稻田环境中结合态磷化氢(MBP)的检测。结果表明:当冷阱温度为-90℃,载气流量为1.5 mL/min,柱温箱温度为90℃,检测器温度为220℃时,系统操作条件最优。冷阱二次富集磷化氢的主要机理是富集毛细管柱(KB-Al2O3/NaSO4)对磷化氢的吸附作用,属气-固吸附。系统检出限为0.041 7 pg,精密度为4.3%。整个水稻生长周期内,水稻土中结合态磷化氢(MBP)的平均含量为120.59 ng/kg,测定结果的相对标准偏差均值为8.5%。该方法对痕量磷化氢的检测效果与使用氮磷检测器(NPD)的传统方法相近,但FID检测器的结构简单、操作方便、价格经济,使环境中痕量磷化氢的检测更容易实现,可推广应用。     

Determination of eighty-one volatile organic compounds in dietary Rumexinduratus leaves by GC/IT-MS, using different extractive techniques

The volatile compounds of Rumexinduratus leaves were studied for the first time. In order to achieve the most complete volatile profile four different extractive techniques (hydrodistillation, solid-phase microextraction, Soxhlet system and direct solvent extraction) were applied. The different extracts were analysed by gas chromatography/ion trap-mass spectrometry (GC/IT-MS) which allowed the identification of 81 compounds, distributed by several chemical classes: esters, terpenes, aldehydes, acids, norisoprenoids, ketones, naphthalene derivatives, steroids derivatives and alcohols, among others. The different techniques lead to different compounds' extraction. Using hexane and dichloromethane, 9 and 4 compounds were extracted, respectively. Hydrodistillation, solid-phase microextraction and Soxhlet extraction allowed the extraction of 43, 24 and 29 compounds, respectively. Hydrodistillation was revealed to be the most effective technique, allowing the extraction of a higher number of compounds, both in the hydrolat (20 compounds) and essential oil (34 compounds), having 11 compounds in common.     

Full-range analysis of ambient volatile organic compounds by a new trapping method and gas chromatography/mass spectrometry

This study investigated the feasibility of analyzing a full range of ambient volatile organic compounds (VOCs) from C(3) to C(12) using gas chromatograph mass spectrometry (GC/MS) coupled with thermal desorption. Two columns were used: a PLOT column separated compounds lighter than C(6) and a DB-1 column separated C(6)-C(12) compounds. An innovative heart-cut technique based on the Deans switch was configured to combine the two column outflows at the ends of the columns before entering the MS. To prevent the resolved peaks from re-converging after combining, two techniques were attempted (hold-up vs. back-flush) to achieve the intended "delayed" elution of heavier components. Thus, the resulting chromatogram covering the full range of VOCs is a combination of two separate elutions, with the heavier section following the lighter section. With the hold-up method, band-broadening inevitably occurred for the delayed C(6)-C(7) DB-1 compounds while the light compounds eluted from the PLOT column. This broadening problem resulted in peak tailing that was largely alleviated by adding a re-focusing stage while the DB-1 compounds were back-flushed, and this modified technique is referred to as the back-flush method. With this modification, the separation of the C(6)-C(7) compounds improved dramatically, as revealed by the decrease in peak asymmetry (As) and increase in resolution. Linearity and precision for these peaks also improved, yielding R(2) and RSD values better than 0.9990 and 2.8%, respectively.     

Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.     

Reaction gas chromatography/mass spectrometry. Part IX: Post-column hydrodesulfurization in capillary GC/MS as an aid in structure elucidation of cyclic sulfides within mixtures

This article describes a method that assists in structure determination of cyclic sulfides mixtures by GC/MS. The method involves the use of a gas-phase hydrodesulfurization microreactor (AP-56 catalyst, reaction temperture 300-315°C, hydrogen as a carrier and reagent gas) located between the capillary column (OV-17) and the mass spectrometer. The presence of a microreactor in such a position does not essentially affect the chromatographic separation achieved by using the capillary column. Combined analysis of the mass spectra registered for the original sulfides and the hydrodesulfurization products permits the structure determination of each effluent to be made more reliably. This is illustrated by the investigation of a reaction mixture containing the structural and geometric isomers of methyl-substituted thiabicyclononanes.     

Determination of complex mixtures of volatile organic compounds in ambient air: an overview

This article reviews developments in the sampling and analysis of volatile organic compounds (VOCs) in ambient air since the 1970s, particularly in the field of environmental monitoring. Global monitoring of biogenic and anthropogenic VOC emissions is briefly described. Approaches used for environmental monitoring of VOCs and industrial hygiene VOC exposure assessments are compared. The historical development of the sampling and analytical methods used is discussed, and the relative advantages and disadvantages of sorbent and canister methods are identified. Overall, there is considerable variability in the reliability of VOC estimates and inventories. In general, canister methods provide superior precision and accuracy and are particulary useful for the analysis of complex mixtures of VOCs. Details of canister methods are reviewed in a companion paper. C. C. Austin is an Invited Scientist of the National Research Council of Canada.     

有机玻璃雕刻过程中有害气体的3阶段预浓缩GC/MS分析

研究了3阶段预浓缩气相色谱-质谱法检测有机玻璃在雕刻过程中排放的有害气体的组成。研究结果表明,气体中含有12种以上的有机污染物。其中甲基丙烯酸甲酯、丙烯酸甲酯、苯、甲苯、苯乙烯等5种有毒有害物可以作为代表该行业特征的污染物加以监控。     

Optimization of analytical quality control for long-term monitoring of metals and volatile organic compounds in groundwater

Statistical analysis of historical results for matrix spikes (MS), matrix spike duplicates (MSD), and laboratory control samples (LCS) from aqueous samples analyzed for metals and volatile organic compounds was performed to determine whether the MS/MSD provided substantive information apart from that provided by the LCS. The statistical analysis showed that the mean recovery of all analytes from MS/MSD closely approximated the mean recovery of all analytes from the LCS. Average bias, skewness, and kurtosis were also assessed for both data sets. The evaluation provided strong evidence for the use of LCS recoveries as performance indicators of probable MS/MSD recoveries of metals and volatile organic compounds from groundwater.     

GC/MS-positive ion chemical ionization and MS/MS study of volatile benzene compounds in five different woods used in barrel making

Extracts from acacia, chestnut, cherry, mulberry, and oak wood, used in making barrels for aging wine and spirits were studied by GC/MS positive ion chemical ionization (PICI). Wood chips were extracted by a 50% water/ethanol solution and a tartrate buffer pH 3.2-12% ethanol (model wine) solution. The principal compounds identified in extracts were guaiacol-containing aldehydes and alcohols, such as benzaldehyde and derivatives, vanillin and syringaldehyde, cinnamaldehyde and coniferaldehyde, eugenol and methoxyeugenol, guaiacol and methoxyguaiacol derivatives. PICI using methane as reagent gas produced a high yield of the protonated molecular ion of volatile phenols, compound identification was confirmed by collision-induced-dissociation (CID) experiments on [M + H](+) species. MS/MS fragmentation patterns were studied with standard compounds: guaiacol-containing molecules were characterized by neutral methyl and methanol losses, benzaldehyde derivatives by CO loss. Acacia wood extracts contained significant syringaldehyde and anisaldehyde, but no eugenol and methoxyeugenol. Significant syringaldehyde, eugenol and methoxyeugenol, and high vanillin were found in chestnut and oak wood extracts; low presence of volatile benzene compounds was found in mulberry wood extracts. Cherry wood extracts were characterized by the presence of several benzaldehyde derivatives and high trimethoxyphenol.     

Multiparametric analysis of amino acids and organic acids in rat brain tissues using GC/MS

Using design of experiment (DOE) theory coupled with multivariate statistical analysis, we have developed a simple and reliable GC/MS-based analytical assay for simultaneous analysis of amino acids and organic acids in rat brain tissue samples. The process of water extraction (pH 10.0) was extensively evaluated using brain tissue samples and a set of 21 reference standards. Acceptable calibration curves were obtained over a wide concentration range, 0.2-35.0 microg/mL for standards and 15.0-2.4 mL/g (tissue) for brain tissue samples. The precision was mostly better than 10% for both the mixed standards and the brain tissue samples. The brain tissue samples exhibited good stability within 48 h with RSD generally less than 15%. Furthermore, the developed analytical method was successfully applied in distinguishing the subtle variation among different parts of the brain tissues, such as cerebral cortex, hippocampus, and thalamus.     

An integrated GC/FT-IR system for the analysis of environmental pollutants

An integrated gas chromatography/Fourier transform infrared spectrometry (GC/FT-IR) system developed for the analysis of environmental pollutants is described. The versatility of the system allows the utilization of many different techniques of sample introduction and manipulation during analysis. The sample can be introduced by direct injection or thermal desorption from an adsorbent cartridge, and can then be separated on one of two capillary columns and detected by FT-IR or an FID. Cold traps and collection cartridges incorporated in the system permit recovery and additional fractionation of samples. Recovered sample and sample fractions can then be re-analyzed by GC/FT-IR or subsequently analyzed by GC/MS or other methods.     

Development of a novel analytical method for determination of chondroitin sulfate using an in-capillary enzyme reaction

A novel analytical method for determination of total amount of chondroitin sulfate (CS) based on its conversion to desulfated chondro-disaccharide via an enzyme-catalyzed reaction, was developed. Using the in-capillary enzyme reaction, the method was also applied to the successful construction of an on-line analytical system. Within this system, electrophoretic migration was used to mix zones containing the enzyme mixture (chondroitinase ABC, chondro-4-sulfatase, chondro-6-sulfatase and 2-o-sulfatase) and the substrate (CS). The reaction was then allowed to proceed in the presence of a weak electric field and, finally, the product (desulfated chondro-disaccharide) of enzyme reaction migrated to the detector under the influence of an applied electric field. A polyvinyl alcohol-coated capillary was used to reduce protein adsorption. Desulfated chondro-disaccharide was successfully migrated toward the anode in 10 mM Tris-acetate buffer (pH 7.0) under reversed polarity and detected at 232 nm. The established method was validated and demonstrated to be applicable in the determination of total amount of CS in a commercial ophthalmic solution. No interference from the formulation excipients was observed. Good linearity was obtained, with correlation coefficients above 0.999. Recoveries and precisions ranged from 100.0 to 100.5%, and from 0.2 to 0.6% of the relative standard deviation, respectively. Good agreement was obtained between the established method and traditional photometric method based on carbazole reaction. In this study, application of the method to disaccharide compositional analysis was also performed.     

Construction of an automated gas chromatography/mass spectrometry system for the analysis of ambient volatile organic compounds with on-line internal standard calibration

An automated sampling and enrichment apparatus coupled with a gas chromatography/mass spectrometry (GC/MS) technique was constructed for the analysis of ambient volatile organic compounds (VOCs). A sorbent trap was built within the system to perform on-line enrichment and thermal desorption of VOCs onto GC/MS. In order to improve analytical precision, calibration accuracy, and to safe-guard the long-term stability of this system, a mechanism to allow on-line internal standard (I.S.) addition to the air sample stream was configured within the sampling and enrichment apparatus. A sub-ppm (v/v) level standard gas mixture containing 1,4-fluorobenzene, chloropentafluorobenzene, 1-bromo-4-fluorobenzene was prepared from their pure forms. A minute amount of this I.S. gas was volumetrically mixed into the sample stream at the time of on-line enrichment of the air sample to compensate for measurement uncertainties. To assess the performance of this VOC GC/MS system, a gas mixture containing numerous VOCs at sub-ppb (v/v) level served as the ambient air sample. Various internal standard methods based on total ion count (TIC) and selective ion monitoring (SIM) modes were attempted to assess the improvement in analytical precision and accuracy. Precision was improved from 7-8% RSD without I.S. to 2-3% with I.S. for the 14 target VOCs. Uncertainties in the calibration curves were also improved with the adoption of I.S. by reducing the relative standard deviation of the slope (Sm%) by an average a factor of 4, and intercept (Sb%) by a factor of 2 for the 14 target VOCs.     

Photooxidation of aqueous trichloroethylene using a buoyant photocatalyst with reaction progress monitored via micro-headspace GC/MS

Although photooxidation has previously been shown to be successful in removing organic contaminants from water, methods combining the rapid photooxidation of the desired contaminant with easy catalyst manipulation and removal are few and far between. In the absence of an easy means of catalyst removal, the photooxidation process becomes more costly and time consuming, and photocatalysis cannot be employed as an in situ method for the remediation of aqueous organic contaminants. In this study, the photocatalyst was added to an aqueous trichloroethylene (TCE) solution in the form of TiO₂-coated buoyant microspheres. The solution, placed in a flow-cell photoreactor along with the buoyant catalyst, was irradiated with a UV-filtered Xenon light source. Limited sample sizes necessitated the development of a low-cost headspace GC/MS analysis method, utilizing a standard direct-injection autosampler. This analytical technique aptly monitored reaction progress and indicated that aqueous TCE concentration decreases by nearly 90% in the first hour of irradiation. Subsequent solvent extraction GC/MS analysis indicated that the TCE is initially sorbed by the photocatalyst spheres, but as irradiation continued, TCE is removed from the catalyst spheres surfaces. During the course of irradiation, the expected TCE mineralization product hydrochloric acid appeared, as indicated by a decrease in pH and ion chromatography analysis. The microsphere-born catalyst was easily removed from the treated solution by filtration. Thus, it is possible that a method for effective, low-cost in situ photooxidation of aqueous organic contaminants will be realized in the near future.     

Two new standard reference materials for the determination of drugs of abuse in human hair

Two new standard reference materials (SRM) for drugs of abuse in human hair have been developed. SRM 2379 consists of hair spiked with cocaine, benzoylecgonine, cocaethylene, phencyclidine, amphetamine, and methamphetamine. SRM 2380 consists of hair spiked with codeine, morphine, monoacetylmorphine, and tetrahydrocannabinol (THC). The SRMs were prepared by soaking the hair in a solution of the target analytes in water-dimethylsulfoxide. The concentration of each analyte was determined using two methods, one based upon gas chromatography/mass spectrometry (GC/MS) and one based upon liquid chromatography/mass spectrometry (LC/MS). Both methods used 0.1 M HCl for extraction of all the analytes from the hair, except for THC, which was extracted with 1 M NaOH. For isolation of the analytes from the extracts, the GC/MS-based methods used different clean-up procedures from those used for the LC/MS-based methods. The results from the two methods were in good agreement with mean differences for the analytes ranging from 4% to 16%. These materials will enable laboratories performing analyses of hair for drugs of abuse to test the accuracy of their methods.     

Development and validation of a sensitive and selective method using GC/MS-MS for quantification of 5-fluorouracil in hospital wastewater

Pollution of the environment by pharmaceuticals is a subject of growing scientific and societal concern. However, few quantitative data have been reported concerning hospital wastewater contamination. Among the different molecules used at hospital, antineoplastic drugs appear to be of special interest, and 5-fluorouracil (5-FU) can be considered as a key compound of this therapeutic class. To monitor this pharmaceutical in hospital wastewater, a highly specific and selective method was developed using gas chromatography tandem mass spectrometry after solid-phase extraction. This sensitive method (limit of quantification = 40 ng L⁻¹) was then applied to assess sewage contamination of a middle-size hospital with oncology service located in Paris, France. Native 5-FU was detectable in 12 of the 14 analysed samples. In positive samples, concentration range was measured from 0.09 to 4.0 μg L⁻¹. Finally, a predicting model for the hospital wastewater concentrations is presented, and results of this model are discussed.     

Development of a pre-concentrator-thermo-desorber/micro-gas chromatograph/mass spectrometer coupling for on-site analyses of emissions of volatile organic compounds from landfills

The development and use of a pre-concentrator-thermo-desorber/micro-gas chromatograph/mass spectrometer (μTD/μGC/MSD) coupling for the on-site analysis of VOCs in landfill gases are presented. The coupling has the advantage of analysing compounds with two detectors operated in series: the TCD (of the μGC) initially analyses the gas without destroying it, and then the MSD identifies the compounds. Due to the TCD response, the results were quantified with reference to toluene. The reliability of the analytical chain for quantitative analysis was validated by sampling two gaseous standards, including the EPA TO14 mixture, containing 39 compounds. With the OV1?μGC column, 24 compounds were identified and 16 correctly quantified. The repeatability of the measures estimated by their standard deviation was in the order of 1–2%. The detection limit was evaluated at 0.1?ppbv, for a 40?min pre-concentration on the Tenax of the μTD. The results of VOC analyses in the air of a landfill site obtained with the μTD/μGC/MSD coupling show its potential for on-site analyses: immediate results, high sensitivity, no storage for the samples, and measurements of pollution peaks.