Rapid headspace solid-phase microextraction-gas chromatographic-time-of-flight mass spectrometric method for qualitative profiling of ice wine volatile fraction. I. Method development and optimization

An analytical method for the determination of volatile and semi-volatile compounds representing various chemical groups in ice wines was developed and optimized in the presented study. A combination of the fully automated solid-phase microextraction (SPME) sample preparation technique and gas chromatographic-mass spectrometric (GC-MS) system to perform the final chromatographic separation and identification of the analytes of interest was utilized. A time-of-flight mass spectrometric (TOF-MS) analyzer provided very rapid analysis of this relatively complex matrix. Full spectral information in the range of m/z 35-450 was collected across the short GC run (less than 5 min). Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS) 50/30 microm fiber performed best during the optimization experiments and it was used in the headspace SPME mode to isolate compounds from ice wine samples, consisting of 3 mL wine with 1g salt addition. After the sample incubation and extraction (both 5 min at 45 degrees C), analytes were thermally desorbed in the GC injector for 2 min (injector maintained at 260 degrees C) and transferred into the column. The MS data acquisition rate of 50 spectra/s was selected as optimal. The optimized analytical method did not exceed 20 min per sample, including both the isolation and pre-concentration of the analytes of interest, the final GC-TOF-MS analysis and the fiber bake-out. Both a linear temperature-programmed retention index (LTPRI) method using C(8)-C(20) alkanes loaded onto the fiber and a mass spectral library search were employed to identify the target compounds. The repeatability of the developed and optimized HS-SPME-GC-TOF-MS method for ice wine analysis, expressed as relative standard deviation (RSD, %, n=7), ranged from 3.2 to 9.0%.     

气相色谱-单光子电离飞行时间质谱的联用及在柴油组分表征中的应用

建立了一种气相色谱(GC)与单光子电离-飞行时间质谱(SPI-TOF MS)联用(GC/SPI-TOF MS)的分析方法。首先,设计了一种双层套管的传输管用于连接GC与SPI-TOF MS,实现了GC与单光子电离离子源的无缝连接。在此基础上,以n-十五烷标准品和苯/甲苯/二甲苯的标准气为对象,对电离源的重要电压参数进行了优化,得到了纯净的分子离子峰,实现了对各类有机物的快速和准确定性。最后,将该方法用于分析柴油中的挥发性与半挥发性有机物,获得了柴油组分的二维GC×SPI-TOF MS谱图。不需要复杂的谱图解析和数据处理,根据谱图中离子的质荷比(m/z)归纳了柴油的主要成分,包括脂肪烃、芳香烃和含量很低的苯并吡咯等含氮化合物;根据色谱的保留时间将柴油中的同分异构体区分开来。结果表明GC/SPI-TOF MS法是一种简单、有效的分析方法,非常适于柴油及复杂环境样品等的分析表征。     

Temperature requirements for thermal modulation in comprehensive two-dimensional gas chromatography

Temperature requirements for trapping and release of compounds in a cryogenic gas loop-type GC x GC modulator were determined. Maximum trapping temperatures on the uncoated, deactivated modulator capillary were determined for compounds from C4 (bp -0.5 degrees C) to C40 (bp 522 degrees C). The liquid-nitrogen cooled gas flow rate was reduced from a high of 15.5 to 1.5 SLPM over the range to achieve the required trapping temperature. Excessive cold jet flow rates caused irreversible trapping and peak tailing for semi-volatile compounds above C26. Alternate cold jet coolants were investigated. An ice water-cooled jet was able to trap compounds with boiling points from C18 (bp 316 degrees C) to C40 and a room temperature air-cooled jet was able to trap compounds from C20 (bp 344 degrees C) to C40. The hot jet produced launch temperatures approximately 40 degrees C hotter than the elution temperature with heating time constants of 8 to 27 ms. Modulated compound peaks were symmetrical with half-height peak widths of 43 to 56 ms for compounds with little second column retention, and 70 to 75 ms for compounds with more second column retention. The liquid nitrogen-cooled loop modulator with gas flow programming was used to produce a GC x GC chromatogram for a crude oil that contained compounds from C7 to C47.     

Feasibility of preparing and analyzing gas standards containing heavy hydrocarbons (C10–C16)

State and federal agencies are beginning to monitor ambient air for compounds related to diesel exhaust. The National Institute of Standards and Technology (NIST) was asked to develop standards containing heavy (C10-C16) alkanes which could then be used in air monitoring and exhaust studies. Several primary gravimetric standards, containing heavy (C10-C16) alkanes in nitrogen, were developed and analyzed by gas chromatography (GC) with flame-ionization detection (FID). The results of this research indicate that accurate gas standards containing these hydrocarbons can be prepared. However, the analytical results show that the temperature of the transfer system from the gas cylinder to the GC column (including the gas-sample valve) must be heated in order to prevent adsorption of these compounds within the analytical system. The results indicate that even at elevated temperatures these compounds are being absorbed within the system. The results show that quantitative results cannot be obtained by using one compound such as hexane, as an internal standard to determine the concentration of other hydrocarbons. Quantitative and accurate results are best obtained if standards for each hydrocarbon of interest are used to determine concentrations of unknowns for the respective hydrocarbon.     

A universal temperature controlled membrane interface for the analysis of volatile and semi-volatile organic compounds

A universal temperature controlled membrane interface (TCMI) has been constructed for hollow-fibre membranes. The membrane temperature is controllable in the range -70 to 250 degrees C using an electric heater and a flow of cooled nitrogen or helium gas. Volatile and semi-volatile organic compounds may be detected either by continuous diffusion across the membrane or by in-membrane pre-concentration followed by thermal desorption into the detector. The TCMI interface is demonstrated in combination with mass spectrometry and GC-MS, for the determination of VOCs and SVOCs in aqueous and air samples and for the on-line monitoring of a bioreactor.     

Development and validation of a method for air-quality and nuisance odors monitoring of volatile organic compounds using multi-sorbent adsorption and gas chromatography/mass spectrometry thermal desorption system

An analytical method based on thermal desorption (TD) coupled to gas chromatography (GC) and mass spectrometry detection (MS) has been developed and validated for the determination of a wide range of odor nuisance and air-quality volatile organic compounds (VOC) in air. New generation isocyanates, isocyanato- and isothiocyanatocyclohexane, have been included for the first time as target compounds due to their high occurrence in air samples. A dynamic air sampling method to trap gas and vapor on multi-sorbent tubes using portable pump equipment has been also developed. Sorbent tubes were filled with Carbotrap (70mg), Carbopack X (100mg) and Carboxen-569 (90mg). Validation of the TD-GC-MS method showed good selectivity, sensibility and precision according to Compendium Method TO-17 (US Environment Protection Agency) criteria. Limits of detection (signal-to-noise=3, ng in tube) ranges were 0.004-0.03ng (alcanes), 0.001-0.1ng (aromatics), 0.03-14ng (aldehydes), 0.003-7ng (alcohols), 0.003-0.04ng (chlorides), 0.02-0.5ng (esters), 0.002-0.1ng (ketones), 0.01-0.53ng (terpenes), 14-97ng (amides), 0.2-10ng (isocyanates) and 0.001ng (carbon disulfide). The linear dynamic range was over 3-5 orders of magnitude, depending of the VOC. TD-GC-MS analysis was reproducible, with relative standard deviation (n=5) within 20%. VOCs breakthrough examination showed no significant losses when about 2000ng standard was prepared. In order to evaluate the performance of the developed method on real samples, several industrial and urban air samples were analysed. VOCs were found to be stable on the sorbent tubes for at least 1 week when stored at 4 degrees C.     

Trace analysis for chlorinated hydrocarbons in air by quantitative combustion and coulometric chloride determination: application to standardization of vinyl chloride permeation tubes

Methods for high-temperature combustion of vinyl chloride in air were studied theoretically and two types of gas mixtures were found to give 100% conversion into HCl. The chloride was determined by coulometric titration with silver, in 70% acetic acid. Good agreement between theoretical and experimental results was obtained. Permeation rates of vinyl chloride from fluorinated ethylene propylene permeation tubes were determined gravimetrically and with the coulometric method developed. The standard deviations of the methods were 0.002 and 0.001 microg min respectively for permeation rates of 0.5 microg min when the temperature was controlled to +/- 0.02 degrees . The coulometric mean value was 99.9% of the gravimetric mean; 1 ppm of vinyl chloride in air could be determined coulometrically with a standard deviation of about 0.002 ppm.     

Measurement of semi-volatile azaarenes in airborne particulate and vapor phase

In the atmosphere, exchanges between the gas and particle phases has a profound influence on the removal processes and residence times of semi-volatile compounds. This study describes analytical procedures for the reliable quantitation of both gas and particle phase azaarenes (two-, three- and four-rings). Samples of particulate material were collected on the glass fiber filters and gas phase material on polyurethane foam plugs. Azaarene compounds were isolated utilizing an acid/base partition method. Isolated azaarenes compounds were then characterized and quantified using gas chromatography with mass spectrometry (GC/MS). The analytical method described in this paper is the first procedure for the simultaneous determination of gas and particle phase azaarenes and allows 47 azaarene compounds to be reliably quantified despite the complexity of urban aerosols.     

Short metal capillary columns packed with polymer-coated fibrous materials in high-temperature gas chromatography

The high-temperature gas chromatographic (GC) separation of several semivolatile compounds is studied with a short metal capillary column packed with fibrous material, having a polydimethylsiloxane coating thereon. Taking advantage of the excellent heat-resistance of the fiber and also the combination of the surface-deactivated metal capillary, a temperature-programmed separation up to 450 degrees C is successfully demonstrated for the separation of polymer standard samples. The average molecular weight of the commercially-available polymer standard samples for size exclusion chromatography (SEC) is estimated by high-temperature GC analysis and compared with the nominal value determined by a conventional SEC method. Although a slight deviation for the number-average molecular weight is observed between the GC and SEC analysis, the data for the weight-average molecular weight shows a good agreement in these methods. The results also suggest the future possibility of the fiber-packed metal capillary as a miniaturized GC column with an increased sample loading capacity.     

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.     

顶空气相法测定氯乙烯生产过程产生的盐酸溶液中的乙炔和氯乙烯

 采用顶空气相法测定了氯乙烯生产过程产生的盐酸溶液中的乙炔和氯乙烯。使用氢氧化钠将试样中的氯化氢中和 ,从而消除其在气相分析乙炔和氯乙烯中的影响。顶空平衡温度为 35℃ ,平衡时间为 4 5min ,柱为填充了GDX 2 0 2固定相的 2m× 3mmi d 不锈钢柱 ,柱温 14 0℃。顶空气体进样量为 1mL。以外标法定量 ,乙炔含量测定结果的相对标准偏差为 0 85 % ;当其含量为 30 0 μg/g～ 15 0 μg/g时 ,回收率为 98 9%～10 3%。氯乙烯含量测定结果的相对标准偏差为 1 4 % ;当其含量为 2 0 0 μg/g～ 10 0 μg/g时 ,回收率为 98 8%～10 2 %。     

Characterization of a commercial gas chromatography-flame ionization detection system for the in situ determination of C5-C10 hydrocarbons in ambient air

A commercial automated gas chromatograph with preconcentration on solid adsorbents (AirmoVoc HC1010) was coupled with a mass spectrometer in parallel with the flame ionization detection (FID) system and characterized for its suitability for quasi continuous measurements of atmospheric hydrocarbons (HCs) with a time resolution of 20 min. Of the 50 identified HCs in the range C5-C10, 15 elute in isolated peaks and 20 in groups of two or more HCs. The remaining 15 HCs suffer from coelution by oxygenated and halogenated compounds. Procedures to minimize and quantify the blanks and the memory from the adsorbents are described. Calibration was based on a custom-made diffusion source. The accuracy of this calibration (+/-10%, 2sigma) was verified by analysis of a certified 70-component standard (average deviation: -4.3+/-2%). During a field experiment in Summer 1998, the HC1010 system was compared with a custom-made GC system with cryogenic preconcentration and much better separation properties but lower time resolution. In ambient air, good agreement (2sigma deviation <14% or 10 ppt) was found for HCs and groups of HCs that are free from coelution with oxygenated compounds, whereas large discrepancies (in some cases more than a factor of three) were found for those HCs that coelute with oxygenated compounds, as identified by MS. Analysis of the mass spectra from those peaks via specific target ions showed much better agreement with the FID system of the reference GC within 25%.     

Trace analysis of organics in air by corona discharge atmospheric pressure ionization using an electrospray ionization interface

A corona discharge ion source operating at atmospheric pressure in the point-to-plane configuration was constructed by reconfiguring the ion source of a commercial electrospray ionization (ESI) quadrupole mass spectrometer. This new source allows direct air analysis without modification to the mass spectrometer. Detection and quantitation of semi-volatile compounds in air is demonstrated. The analytical performance of the system was established using the chemical warfare agent simulants methyl salicylate and dimethyl methylphosphonate. Limits of detection are 60 pptr in the negative-ion mode and 800 pptr in the positive-ion mode for methyl salicylate and 800 pptr in the negative-ion mode and 3.6 ppb in the positive-ion mode for dimethyl methylphosphonate. A linear response was observed from 60 pptr to 8 ppb for methyl salicylate in air in the negative-ionization mode. Cluster ion formation versus production of analyte ions was investigated and it was found that dry air or an elevated capillary interface temperature (130 degrees C) was needed to avoid extensive clustering, mostly of water. Reagent gases are not needed as proton sources, as is usually the case for atmospheric pressure chemical ionization, and this, together with the simplicity, sensitivity and speed of the technique, makes it promising for miniaturization and future field studies.     

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.     

化工废渣中半挥发性有机有害物的GC/MS分析

 参照美国环保局的８２７０方法，根据我国情况采用内标定量法对某化工废渣进行半挥发性有机物分析，使用内标法可消除系统和进样过程中带来的误差，提高数据的置信度。通过实验，测得废渣中含１０种美国环保局规定的优先监测污染物和１１种含氯化合物，含量在０．４～８０μｇ／ｇ之间。它们对人体有较大危害，必须进行严格处理才能排放。     

Development of an electrothermal vaporization ICP-MS method and assessment of its applicability to studies of the homogeneity of reference materials

A method has been developed for measurement of the homogeneity of analyte distribution in powdered materials by use of electrothermal vaporization with inductively coupled plasma mass spectrometric (ETV-ICP-MS) detection. The method enabled the simultaneous determination of As, Cd, Cu, Fe, Mn, Pb, and Zn in milligram amounts of samples of biological origin. The optimized conditions comprised a high plasma power of 1,500 W, reduced aerosol transport flow, and heating ramps below 300 degrees C s(-1). A temperature ramp to 550 degrees C ensured effective pyrolysis of approximately 70% of the organic compounds without losses of analyte. An additional hold stage at 700 degrees C led to separation of most of the analyte signals from the evaporation of carbonaceous matrix compounds. The effect of time resolution of signal acquisition on the precision of the ETV measurements was investigated. An increase in the number of masses monitored up to 20 is possible with not more than 1% additional relative standard deviation of results caused by limited temporal resolution of the transient signals. Recording of signals from the nebulization of aqueous standards in each sample run enabled correction for drift of the sensitivity of the ETV-ICP-MS instrument. The applicability of the developed method to homogeneity studies was assessed by use of four certified reference materials. According to the best repeatability observed in these sample runs, the maximum contribution of the method to the standard deviation is approximately 5% to 6% for all the elements investigated.     

Dynamic system for the calibration of semi-volatile carbonyl compounds in air

A dynamic calibration system designed for generating accurate and precise concentrations of semi-volatile carbonyls in the ppb (v/v) (ppbv)-ppt (v/v) (pptv) range has been developed and tested. Alkanals from C6 to C9 were used as test compounds. Diffusion rates of their vapours from capillary tubes were determined theoretically and with two methods whose accuracy was independently evaluated with liquid standard solutions. Methods selected for testing the calibration system were those commonly used for the selective quantification of carbonyls in air. One is based on the well-known reaction with 2,4-dinitrophenylhydrazine (DNPH), followed by the analysis of formed hydrazones by HPLC-UV. The other is based on the retention of carbonyls on graphitic carbon adsorbents, followed by MS detection of the sample injected into a capillary column by thermal desorption. A good consistency was found between the values of the diffusion rates determined by the two methods. The scatter between the two methods was in the range of +/-10% when diffusion rates of ca. 1 ng/s were attained. Experimental values closely approached those calculated by applying the equation describing the diffusion of a vapour in equilibrium with the liquid through a capillary tube.     

Gas chromatography/ion trap mass spectrometry applied for the determination of polybrominated diphenyl ethers in soil

A gas chromatography/ion trap mass spectrometry (GC/ITMS) method was developed for the determination of polybrominated diphenyl ethers (PBDEs). ITMS parameters were optimized in order to achieve the best sensitivity for the PBDE analysis. Tandem mass spectrometry, along with an isotope dilution internal standard method, was used for the quantitation. Chromatographic windows were developed for mono- to hepta-BDEs, depending on the retention times when a 30-m GC column was used. A different 15-m column was used to analyze deca-BDE. Environmental soil samples collected from an electronic waste recycling site were prepared by using Soxhlet extraction and column chromatographic cleanup. Average recoveries of 61-118% were obtained for the 13C-labeled PBDE internal standards spiked in the samples prior to sample preparation. The accuracy represented by relative analytical errors was -24% to 18%, and the precision (relative standard deviation) was 11-26% (n=8). The method detection limits ranged from 0.013-0.25 ng/g for the PBDEs in soil.     

Online in situ analysis of selected semi-volatile organic compounds in water by automated microscale solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A fully automated analytical method was developed for the online in situ analysis of selected semi-volatile organic compounds in water. The method used a large-volume injection/gas chromatography/mass spectrometry coupled with a fully automated microscale solid-phase extraction technique, which was based on x-y-z robotic techniques. Water samples were extracted by using a 96-well solid-phase extraction plate. For most analytes included in this study, the obtained linear calibrations ranged from 0.05 to 5.0 microg/L with correlation coefficients of 0.996-1.000, the method detection limits were less than 0.1 microg/L, and the relative recoveries were in the range of 70-120% with a relative standard deviation of less than 15% for fortified reagent water samples. The applications to chlorinated tap water, well water, and river water have been validated. The obtained results were similar to those resulting from fortified reagent water samples for all analytes except metribuzin, bromacil, aldrin, and methoxychlor. Matrix effects were observed for these analytes. In general, this fully automated analytical method was rugged, reliable, and easy to operate, and was capable of providing real-time data to water treatment and distribution systems as well as water reservation and protection systems. In addition, the method could reduce the analytical costs associated with sample collection, transportation, storage, and preparation.